ATOPCV1 5 0 Quantum Mechanics II

CHAPTER 5
Quantum Mechanics – II
 Schrodinger Wave Equation for a Particle in a Three Dimensional Box
In the first chapter of this book, we derived and discussed the Schrodinger wave equation for a particle
in the one-dimensional box. In this chapter, we will extend that procedure to the particle in a three-dimensional
box. In order to do so, consider a particle trapped in a 3-dimensional box of length, breadth, and height as a, b
and c, respectively. This means that this particle can travel in any direction i.e. along x-, y- and z-axis. The
potential inside the box is 0, while outside to the box it is infinite.
Figure 1. The particle in a three-dimensional box.
So far we have considered a quantum mechanical system of a particle trapped in a three-dimensional box. Now
suppose that we need to find various physical properties associated with different states of this system. Had it
been a classical system, we would use simple formulas from classical mechanics to determine the value of
different physical properties. However, being a quantum mechanical system, we cannot use those expressions
because they would give irrational results. Therefore, we need to use the postulates of quantum mechanics to
evaluate various physical properties.
Let ψ be the function that describes all the states of the particle in a three-dimensional box. At this
point we have no information about the exact mathematical expression of ψ; nevertheless, we know that there
is one operator that does not need the absolute expression of wave function but uses the symbolic form only,
the Hamiltonian operator. The operation of Hamiltonian operator over this symbolic form can be rearranged
to give to construct the Schrodinger wave equation; and we all know that the wave function as well the energy,
both are obtained as this second-order differential equation is solved. Mathematically, we can say that
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212 A Textbook of Physical Chemistry – Volume I
̂ 𝜓 = 𝐸𝜓
𝐻 (1)
After putting the value of three-dimensional Hamiltonian in equation (1), we get
−ℎ2 𝜕 2 𝜕2 𝜕2 (2)
[ 2 ( 2 + 2 + 2 ) + 𝑉] 𝜓 = 𝐸𝜓
8𝜋 𝑚 𝜕𝑥 𝜕𝑦 𝜕𝑧
or
−ℎ2 𝜕 2 𝜓 𝜕 2 𝜓 𝜕 2 𝜓 (3)
( + + ) + 𝑉𝜓 = 𝐸𝜓
8𝜋 2 𝑚 𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2
−ℎ2 𝜕 2 𝜓 𝜕 2 𝜓 𝜕 2 𝜓 (4)
( + + ) + 𝑉𝜓 − 𝐸𝜓 = 0
8𝜋 2 𝑚 𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2
or
𝜕 2 𝜓 𝜕 2 𝜓 𝜕 2 𝜓 8𝜋 2 𝑚 (5)
+ + + (𝐸 − 𝑉)𝜓 = 0
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2 ℎ2
The above-mentioned second order differential equation is the Schrodinger wave equation for a particle
moving along three dimensions. Since the conditions outside and inside the box are different, the equation (5)
must be solved separately for both cases.
1. The solution of Schrodinger wave equation for outside the box: After putting the value of potential
outside the box in equation (5) i.e. V = ∞, we get
𝜕 2 𝜓 𝜕 2 𝜓 𝜕 2 𝜓 8𝜋 2 𝑚 (6)
+ + + (𝐸 − ∞)𝜓 = 0
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2 ℎ2
Since E is negligible in comparison to the ∞, the above equation becomes
𝜕2𝜓 𝜕2𝜓 𝜕2𝜓 (7)

+ + − ∞𝜓 = 0
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2
𝜕2𝜓 𝜕2𝜓 𝜕2𝜓 (8)

∞𝜓 = + +
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2
1 𝜕2𝜓 𝜕2𝜓 𝜕2𝜓 (9)

𝜓= ( + + )=0
∞ 𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2
The physical significance of the equation (9) is that the particle cannot go outside the box, and is always
reflected back when it strikes the boundaries. In other words, as the function describing the existence of
particles is zero outside the box, the particle cannot exist outside the box.
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CHAPTER 5 Quantum Mechanics – II 213
2. The solution of Schrodinger wave equation for inside the box: After putting the value of potential inside
the box in equation (5) i.e. V = 0, we get
𝜕 2 𝜓 𝜕 2 𝜓 𝜕 2 𝜓 8𝜋 2 𝑚 (10)
+ + + (𝐸 − 0)𝜓 = 0
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2 ℎ2
𝜕 2 𝜓 𝜕 2 𝜓 𝜕 2 𝜓 8𝜋 2 𝑚𝐸 (11)
+ + + 𝜓=0
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2 ℎ2
The above equation has three variables and is difficult to solve directly. Therefore, it is better to separate
variable, we already know the steps to solve a one-variable equation. To do so, consider that the wave function
ψ is the multiplication of three individual functions as
𝜓(𝑥, 𝑦, 𝑧) = 𝜓(𝑥) × 𝜓(𝑦) × 𝜓(𝑧) = 𝑋𝑌𝑍 (12)
Using the above expression in equation (11), we get
𝜕 2 𝑋𝑌𝑍 𝜕 2 𝑋𝑌𝑍 𝜕 2 𝑋𝑌𝑍 8𝜋 2 𝑚𝐸 (13)

+ + + 𝑋𝑌𝑍 = 0
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2 ℎ2
From the rules of partial derivative, the equation (13) takes the form
𝜕2𝑋 𝜕2𝑌 𝜕 2 𝑍 8𝜋 2 𝑚𝐸 (14)

𝑌𝑍 + 𝑋𝑍 + 𝑋𝑌 + 𝑋𝑌𝑍 = 0
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2 ℎ2
Now divide the above equation by XYZ on both side i.e.
1 𝜕 2 𝑋 1 𝜕 2 𝑌 1 𝜕 2 𝑍 8𝜋 2 𝑚𝐸 (15)
+ + + =0
𝑋 𝜕𝑥 2 𝑌 𝜕𝑦 2 𝑍 𝜕𝑧 2 ℎ2
Assuming
8𝜋 2 𝑚𝐸 (16)
𝑘2 =
ℎ2
The equation (15) becomes
1 𝜕2𝑋 1 𝜕2𝑌 1 𝜕2𝑍 (17)

+ + + 𝑘2 = 0
𝑋 𝜕𝑥 2 𝑌 𝜕𝑦 2 𝑍 𝜕𝑧 2
Also fragmenting the constant 𝑘 2 along three x-, y- and z-axis i.e. 𝑘 2 = 𝑘𝑥2 + 𝑘𝑦2 + 𝑘𝑧2, the equation (17) can
1 𝜕2𝑋 1 𝜕2𝑌 1 𝜕2𝑍 (18)

+ + + 𝑘𝑥2 + 𝑘𝑦2 + 𝑘𝑧2 = 0
𝑋 𝜕𝑥 2 𝑌 𝜕𝑦 2 𝑍 𝜕𝑧 2
The above equation can be written as the sum of three equations with only one variable in each i.e.
no watermark.
𝜕2𝑋 (19)
+ 𝑘𝑥2 𝑋 = 0
𝜕𝑥 2
𝜕2𝑌 (20)
+ 𝑘𝑦2 𝑌 = 0
𝜕𝑦 2
𝜕2𝑍 (21)
+ 𝑘𝑧2 𝑍 = 0
𝜕𝑧 2
The equations (19-21) are simple one-dimensional differential equations whose solutions can be obtained just
like in the one-dimensional box. The solution of equation (19) will give the x-dependent wave function as well
the energy distribution along x-axis i.e.
(22)
2 𝑛𝑥 𝜋𝑥 𝑛𝑥2 ℎ2
𝜓𝑛𝑥 (𝑥) = 𝑋 = √ 𝑆𝑖𝑛 𝑎𝑛𝑑 𝐸𝑛𝑥 =
𝑎 𝑎 8𝑚𝑎2
Similarly, the solution of equation (20) will be
(23)
2 𝑛𝑦 𝜋𝑦 𝑛𝑦2 ℎ2
𝜓𝑛𝑦 (𝑦) = 𝑌 = √ 𝑆𝑖𝑛 𝑎𝑛𝑑 𝐸𝑛𝑦 =
𝑏 𝑏 8𝑚𝑏 2
Just like the above two, the solution of equation (21) will be
(24)
2 𝑛𝑧 𝜋𝑧 𝑛𝑧2 ℎ2
𝜓𝑛𝑧 (𝑧) = 𝑍 = √ 𝑆𝑖𝑛 𝑎𝑛𝑑 𝐸𝑛𝑧 =
𝑐 𝑐 8𝑚𝑐 2
After putting the expressions of individual wave functions from equation (22-24) in equation (12), the total
wave function can be obtained i.e.
(25)
8 𝑛𝑥 𝜋𝑥 𝑛𝑦 𝜋𝑦 𝑛𝑧 𝜋𝑧
𝜓𝑛𝑥 𝑛𝑦 𝑛𝑧 (𝑥, 𝑦, 𝑧) = √ 𝑆𝑖𝑛 𝑆𝑖𝑛 𝑆𝑖𝑛
𝑎𝑏𝑐 𝑎 𝑏 𝑐
Since 𝑘 2 = 𝑘𝑥2 + 𝑘𝑦2 + 𝑘𝑧2, the total energy must be the sum of individual energies i.e.
𝑛𝑥2 𝑛𝑦2 𝑛𝑧2 ℎ2 (26)

𝐸𝑛𝑥 𝑛𝑦 𝑛𝑧 = ( + + )
𝑎2 𝑏 2 𝑐 2 8𝑚
Where 𝑛𝑥 , 𝑛𝑦 , 𝑛𝑦 are the discrete variable whose permitted values from boundary conditions can be 0, 1, 2, 3,
4….∞. Nevertheless, it is worthy to note that even though the n = 0 is permitted by the boundary conditions,
we still don’t use it in equation (25); which is obviously because it makes the whole function zero.
no watermark.
 The Concept of Degeneracy Among Energy Levels for a Particle in Three

Dimensional Box
The solution of Schrodinger wave equation for a particle of mass ‘m’ trapped in three dimensional of
sides a, b and c with zero potential inside and infinite potential outside provide the total wave function ψ as
(27)
𝜓𝑛𝑥 𝑛𝑦 𝑛𝑧 (𝑥, 𝑦, 𝑧) = √ 𝑆𝑖𝑛 𝑆𝑖𝑛 𝑆𝑖𝑛
𝑎𝑏𝑐 𝑎 𝑏 𝑐
Where 𝑛𝑥 , 𝑛𝑦 , 𝑛𝑦 are the discrete variable whose permitted values from boundary conditions can be 1, 2, 3,
4….∞. The variable x, y and z represent the position of the particle along the corresponding axis. Besides, the
expression for total energy is
𝑛𝑥2 𝑛𝑦2 𝑛𝑧2 ℎ2 (28)

𝐸𝑛𝑥 𝑛𝑦 𝑛𝑧 = ( 2 + 2 + 2)
𝑎 𝑏 𝑐 8𝑚
For a cubical box, all the sides become equal (a = b = c). Using this condition in equation (27), the total wave
function representing different quantum mechanical states take the following form.
(29)
𝜓𝑛𝑥 𝑛𝑦 𝑛𝑧 (𝑥, 𝑦, 𝑧) = √ 3 𝑆𝑖𝑛 𝑆𝑖𝑛 𝑆𝑖𝑛
𝑎 𝑎 𝑎 𝑎
Similarly, the energy expression also changes to
ℎ2 (30)
𝐸𝑛𝑥 𝑛𝑦 𝑛𝑧 = (𝑛𝑥2 + 𝑛𝑦2 + 𝑛𝑧2 )
8𝑚𝑎2
Now, in order to define various quantum mechanical states, we need to put valid set quantum numbers. The
expression for first quantum mechanical and corresponding energy can be obtained by putting 𝑛𝑥 = 𝑛𝑦 =
𝑛𝑧 = 1 in equations (29–30) i.e.
(31)
8 𝜋𝑥 𝜋𝑦 𝜋𝑧 3ℎ2
𝜓111 = √ 3 𝑆𝑖𝑛 𝑆𝑖𝑛 𝑆𝑖𝑛 and 𝐸111 =
𝑎 𝑎 𝑎 𝑎 8𝑚𝑎2
Similarly, the next state with energy can be obtained by putting 𝑛𝑥 = 𝑛𝑦 = 1 and 𝑛𝑧 = 2 in equations (29–
30) i.e.
(32)
8 𝜋𝑥 𝜋𝑦 2𝜋𝑧 6ℎ2
If 𝑛𝑥 = 𝑛𝑧 = 1 and 𝑛𝑦 = 2; the wavefunction and energy become

(33)
8 𝜋𝑥 2𝜋𝑦 𝜋𝑧 6ℎ2
If 𝑛𝑦 = 𝑛𝑧 = 1 and 𝑛𝑥 = 2, the state with energy becomes
(34)
8 2𝜋𝑥 𝜋𝑦 𝜋𝑧 6ℎ2
It can be clearly seen that three quantum mechanical states 𝜓112 , 𝜓121 and 𝜓211 possess the same amount of
energy (i.e. 6ℎ2 /8𝑚𝑎2 ); and therefore, are said to be degenerate. In other words, there are three different ways
of existence of the particle inside the box so that the particle possesses 6ℎ2 /8𝑚𝑎2 energy as total.
Figure 2. The energy level diagram representing different quantum mechanical states (in the units of
ℎ2 /8𝑚𝑎2 ) for a particle trapped in a cubical box.
Hence, the degeneracy of the ground state is one i.e. there is only one way for the particle to exist in the box
to create zero-point energy (3ℎ2 /8𝑚𝑎2 ). On the other hand, the degeneracy of first excited stated is 3 as 𝜓112 ,
𝜓121 and 𝜓211, all have 6 units of energy. Moreover, after careful examination of energy diagram, it can be
concluded that degeneracy is 1 if 𝑛𝑥 = 𝑛𝑦 = 𝑛𝑧 , 3 if 𝑛𝑥 = 𝑛𝑦 or 𝑛𝑦 = 𝑛𝑧 or 𝑛𝑥 = 𝑛𝑧 , and 6 if 𝑛𝑥 ≠ 𝑛𝑦 ≠ 𝑛𝑧 .
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 Schrodinger Wave Equation for a Linear Harmonic Oscillator & Its

Solution by Polynomial Method
A diatomic molecule is the quantum-mechanical analog of the classical version of the harmonic
oscillator. It represents the vibrational motion and is one of the few quantum-mechanical systems for which
an exact solution is available. In this section, we will discuss the classical and quantum mechanical oscillator
and their comparative study.
 The Classical Treatment of Simple Harmonic Oscillator
In order to understand the vibrational states of a simple diatomic molecule, we must understand the
classical oscillator first. In order to do so, consider a spring of length r in which a displacement ‘x’ is
incorporated by expending or compressing it.
Figure 2. The pictorial representation of the displacement-inducing in a typical spiral.
For a moment, imagine that the spiral is extended by a displacement of ‘x’; then the restoring force (F)
developed in the spiral can be obtained using Hook’s law as
𝐹 = −𝑘𝑥 (35)
Where k is the constant of proportionality. The minus sign is because the restoring force and the displacement
both are vector quantity but in the opposite direction. In other words, if we expend the spiral, the spiral will
try to compress itself and vice-versa. From equation (35), it seems that the restoring force depends only upon
displacement induced only, however, it is found that stronger spirals have larger restoring force than the weaker
ones for the same magnitude of displacement, indicating a lager force constant. Therefore, the physical
significance of the force constant lies in the fact that it can be used to comment on the strength of oscillator.
Since the potential energy in this expended state is simply the amount of work done in the process of
incorporating the displacement ‘x’, we need calculate the same for further analysis. The restoring force is
proportional to the displacement, and therefore, is a variable quantity; suggesting that we need to carry out the
integration force curve vs displacement. Suppose that the total displacement “x” is fragmented in very small

“dx” segments. The amount of work done in inducing ‘dx’ displacement will be ‘dw’ and can be given by the
following relation
𝑑𝑤 = 𝐹. 𝑑𝑥 (36)
The total work from zero displacement to ‘x’ displacement will be

𝑥
(37)
𝑊 = ∫ 𝐹. 𝑑𝑥
0
𝑥
(38)
= ∫ −𝑘𝑥. 𝑑𝑥
0
𝑥2
𝑥
(39)
= −𝑘 [ ]
2 0
1 (40)
𝑊 = − 𝑘𝑥 2
2
Since there is no electrostatic attraction, the potential energy (V) of the system at displacement will simply be
1 (41)
𝑉 = 𝑘𝑥 2
2
The above equation represents a parabolic behavior and shows that the potential energy varies continuously
with the displacement. Larger the displacement, higher will be the potential energy.
Figure 3. The variation of potential energy as a function of displacement in a classical oscillator.
no watermark.
If ‘m’ is the reduced mass of the diatomic molecule, the equilibrium vibrational frequency ‘ν’ of the oscillator
can be given as
(42)
1 𝑘
𝜈= √
2𝜋 𝑚
Where m is the reduced mass defined by the ratio of the product to the sum of individual masses i.e. 𝑚 =
𝑚1 𝑚2 /(𝑚1 + 𝑚2 ). It is obvious that the energy levels of a simple harmonic oscillator in classical mechanics
are continuous (including zero), and have a limit over the expansion and compression for each value.
Furthermore, the classical oscillator is bound to spend most of its time in the extreme state (fully compressed
and fully expended) and the least time in the equilibrium position.
 The Quantum Mechanical Treatment of Simple Harmonic Oscillator
In order to find out the quantum mechanical behavior of a simple harmonic oscillator, assume that
all the vibrational states can be described by a mathematical expression ψ. Since we don’t know the exact
nature of ψ, we need to follow the postulates of quantum mechanics. Therefore, after applying the Hamiltonian
operator over this symbolic wave function, we have
𝐻𝜓 = 𝐸𝜓 (43)
−ℎ2 𝜕 2 (44)
( + 𝑉) 𝜓 = 𝐸𝜓
8𝜋 2 𝑚 𝜕𝑥 2
or
−ℎ2 𝜕 2 𝜓 (45)
+ 𝑉𝜓 − 𝐸𝜓 = 0
8𝜋 2 𝑚 𝜕𝑥 2
Rearranging, we have
𝜕 2 𝜓 8𝜋 2 𝑚 (46)
+ (𝐸 − 𝑉)𝜓 = 0
𝜕𝑥 2 ℎ2
After putting the value of potential energy form equation (41) in equation (46), we get
𝜕 2 𝜓 8𝜋 2 𝑚 1 (47)
2
+ 2
(𝐸 − 𝑘𝑥 2 ) 𝜓 = 0
𝜕𝑥 ℎ 2
Now put the value of k form equation (42) in equation (47) i.e.
𝜕 2 𝜓 8𝜋 2 𝑚 (48)
+ (𝐸 − 2𝜋 2 𝜈 2 𝑚𝑥 2 )𝜓 = 0
𝜕𝑥 2 ℎ2
or
no watermark.
𝜕2𝜓 8𝜋 2 𝑚𝐸 16𝜋 4 𝑚2 𝜈 2 𝑥 2 (49)

+( − )𝜓 = 0
𝜕𝑥 2 ℎ2 ℎ2
After defining constants
8𝜋 2 𝑚𝐸 4𝜋 2 𝑚𝜈 (50)
𝛼= 𝑎𝑛𝑑 𝛽=
ℎ2 ℎ
The equation (49) takes the form
𝜕2𝜓 (51)
+ (𝛼 − 𝛽 2 𝑥 2 )𝜓 = 0
𝜕𝑥 2
or
𝜕2𝜓 (52)
+ (𝛼 − 𝛽𝛽𝑥 2 )𝜓 = 0
𝜕𝑥 2
Now define a new variable 𝑦 = √𝛽𝑥, then we have the derivative as
𝑑𝑦 (53)
= √𝛽
𝑑𝑥
Squaring both side of the equation (53), and then rearranging
𝑑2 𝑦 (54)
=𝛽 𝑜𝑟 𝑑𝑥 2 = 𝑑2 𝑦/𝛽
𝑑𝑥 2
Now put the value of 𝑑𝑥 2 and 𝛽𝑥 2 in equation (52), we get
𝜕2𝜓 (55)
𝛽 + (𝛼 − 𝛽𝑦 2 )𝜓 = 0
𝜕𝑦 2
Dividing the above equation by β, we get
𝜕2𝜓 𝛼 (56)
2
+ ( − 𝑦2) 𝜓 = 0
𝜕𝑦 𝛽
The equation (56) can be solved asymptotically i.e. at very large values of y. Thus, when 𝑦 ≫ 𝛼/𝛽, the equation
(56) becomes
𝜕2𝜓 (57)
− 𝑦2𝜓 = 0
𝜕𝑦 2
The two possible solutions of the above equation are
𝜓 = 𝑒 ±𝑦
2 /2
(58)
no watermark.
2
Nevertheless, only one of them is acceptable because for 𝜓 = 𝑒 +𝑦 /2, the wavefunction becomes infinite as y
tends to approach ∞. Therefore, the only single-valued, continuous and finite solution we left with is
𝜓 = 𝑒 −𝑦
2 /2
(59)
Since the acceptable solution given above is valid only at very large values of y, it is quite reasonable to think
that the exact solution may also contain some pre-exponential part to attain validity at all values of y. Therefore,
after incorporating some y-dependent unknown function ‘F(y)’ in equation (59), we get
𝜓 = 𝐹(𝑦) 𝑒 −𝑦
2 /2
(60)
In order to find the value of F(y), differentiate the equation (60) first i.e.
𝑑𝜓 2 𝑑𝐹 −𝑦2 /2 (61)
= −𝑦𝑒 −𝑦 /2 . 𝐹 + 𝑒
𝑑𝑦 𝑑𝑦
Differentiating again, we get
𝑑2 𝜓 −
𝑦2 2 2 𝑑𝐹 (62)
= [−𝑦. (−𝑦)𝑒 2 . 𝐹(𝑦) + (−1. 𝑒 −𝑦 /2 . 𝐹(𝑦)) + (−𝑦. 𝑒 −𝑦 /2 )]
𝑑𝑦 2 𝑑𝑦
2 /2 𝑑𝐹 2 𝑑2 𝐹
+ [−𝑦. 𝑒 −𝑦 + 𝑒 −𝑦 /2 2 ]
𝑑𝑦 𝑑𝑦
or
𝑑2 𝜓 2 −𝑦2 /2 −𝑦 2 /2 −𝑦 2 /2
𝑑𝐹 −𝑦 2 /2
𝑑2 𝐹 (63)
= 𝑦 𝑒 . 𝐹(𝑦) − 𝑒 . 𝐹(𝑦) − 2𝑦. 𝑒 + 𝑒
𝑑𝑦 2 𝑑𝑦 𝑑𝑦 2
or
𝑑2 𝜓 𝑑2 𝐹 𝑑𝐹 2 (64)
2
= [ 2
− 2𝑦. + (𝑦 2 − 1) 𝐹] 𝑒 −𝑦 /2
𝑑𝑦 𝑑𝑦 𝑑𝑦
Now, after using equation (60) and equation (64) in equation (56), we get
𝑑2 𝐹 𝑑𝐹 2 𝛼 2 (65)
[ 2
− 2𝑦. + (𝑦 2 − 1) 𝐹] 𝑒 −𝑦 /2 + ( − 𝑦 2 ) 𝐹(𝑦) 𝑒 −𝑦 /2 = 0
𝑑𝑦 𝑑𝑦 𝛽
or
𝑑2 𝐹 𝑑𝐹 𝛼 2 (66)
[ 2 − 2𝑦. + ( − 1) 𝐹(𝑦)] 𝑒 −𝑦 /2 = 0
𝑑𝑦 𝑑𝑦 𝛽
2
Now because of the quantity 𝑒 −𝑦 /2 will be zero only at 𝑦 = ±∞, the sum of the terms present in the bracket
must be zero at normal y-values i.e.
no watermark.
𝑑2 𝐹 𝑑𝐹 𝛼 (67)
− 2𝑦. + ( − 1) 𝐹(𝑦) = 0
𝑑𝑦 2 𝑑𝑦 𝛽
The above differential equation is a “Hermit differential equation” and can be solved to find the expression for
the “unknown” function 𝐹(𝑦). The solution of equation (67) can be obtained by the polynomial method by
expressing the function F(y) as a power series in terms of variable ‘y’.
𝐹 = 𝑎0 + 𝑎1 𝑦 + 𝑎2 𝑦 2 + 𝑎3 𝑦 3 + 𝑎4 𝑦 4 … … … … (68)
Differentiating the above equation, we get
𝑑𝐹 (69)
= 𝑎1 + 2𝑎2 𝑦 + 3𝑎3 𝑦 2 + 4𝑎4 𝑦 3 … … … …
𝑑𝑦
Differentiating again, we get
𝑑2 𝐹 (70)
= 2𝑎2 + 6𝑎3 𝑦 + 12𝑎4 𝑦 2 … … … …
𝑑𝑦 2
Using equation (68-70) in equation (67), we get
[2𝑎2 + 6𝑎3 𝑦 + 12𝑎4 𝑦 2 … ] − 2𝑦[𝑎1 + 2𝑎2 𝑦 + 3𝑎3 𝑦 2 + 4𝑎4 𝑦 3 … ] (71)

𝛼
+ ( − 1) [𝑎0 + 𝑎1 𝑦 + 𝑎2 𝑦 2 + 𝑎3 𝑦 3 + 𝑎4 𝑦 4 … ] = 0
𝛽
or
[2𝑎2 + 6𝑎3 𝑦 + 12𝑎4 𝑦 2 … ] − [2𝑎1 𝑦 + 4𝑎2 𝑦 2 + 6𝑎3 𝑦 3 + 8𝑎4 𝑦 4 … ] (72)

𝛼 𝛼 𝛼
+ [( − 1) 𝑎0 + ( − 1) 𝑎1 𝑦 + ( − 1) 𝑎2 𝑦 2 + ⋯ ] = 0
𝛽 𝛽 𝛽
After further rearranging

𝛼 𝛼 (73)
[2𝑎2 + ( − 1) 𝑎0 ] + [6𝑎3 𝑦 − 2𝑎1 𝑦 + ( − 1) 𝑎1 𝑦]
𝛽 𝛽
𝛼
+ [12𝑎4 𝑦 2 − 4𝑎2 𝑦 2 + ( − 1) 𝑎2 𝑦 2 ] + ⋯ = 0
𝛽
or
𝛼 𝛼 (74)
[2𝑎2 + ( − 1) 𝑎0 ] + [6𝑎3 − 2𝑎1 + ( − 1) 𝑎1 ] 𝑦
𝛽 𝛽
𝛼
+ [12𝑎4 − 4𝑎2 + ( − 1) 𝑎2 ] 𝑦 2 + ⋯ = 0
𝛽
The above equation is valid only when coefficients of the individual power of y are zero i.e.
For y0
no watermark.
𝛼 (75)
2𝑎2 + ( − 1) 𝑎0 = 0
𝛽
For y1
𝛼 (76)
6𝑎3 + ( − 1 − 2) 𝑎1 = 0
𝛽
For y2
𝛼 (77)
12𝑎4 + ( − 1 − 4) 𝑎2 = 0
𝛽
Similarly, for yk
𝛼 (78)
(𝑘 + 1)(𝑘 + 2)𝑎𝑘+2 + ( − 1 − 2𝑘) 𝑎𝑘 = 0
𝛽
The above equation can be rearranged for the coefficient 𝑎𝑘+2 i.e.
𝛼
( − 1 − 2𝑘) 𝑎𝑘 (79)
𝛽
𝑎𝑘+2 =−
(𝑘 + 1)(𝑘 + 2)
Where k is an integer. The expression given above is popularly known as the recursion formula, and allows
one to determine the coefficient 𝑎𝑘+2 of the term yk+2 in terms of 𝑎𝑘 -coefficient of the yk term. In simple words,
we can calculate 𝑎2 , 𝑎4 , 𝑎6 etc. in terms of 𝑎0 if we set 𝑎1 = 0; likewise, the coefficients 𝑎3 , 𝑎5 , 𝑎7 etc. can
be obtained in terms of 𝑎1 if we set 𝑎0 = 0.
However, the power series will still be made up of the infinite number of terms, making function F(y)
infinite at 𝑦 = ∞. Therefore, we must restrict the number of terms so that the function remains acceptable.
This can be made possible if, at a certain value of 𝑘 = 𝑛, the numerator in equation (79) becomes zero i.e.
𝛼 𝛼 (80)
− 1 − 2𝑘 = − 1 − 2𝑛 = 0
𝛽 𝛽
or
𝛼 (81)
= 2𝑛 + 1
𝛽
Where 𝑛 = 0, 1, 2, 3 …. etc. The series that is obtained so contains a finite number of terms and is called as
“Hermit polynomial” i.e. 𝐻𝑛 (𝑦). All these Hermit polynomials are generating-function defined and are given
below.
2 𝑑𝑛 −𝑦2 (82)
𝐻𝑛 (𝑦) = (−1)𝑛 . 𝑒 𝑦 . .𝑒
𝑑𝑦 𝑛
no watermark.
For instance, some of the Hermit polynomials for n = 0, 1 and 2 are calculated as given below.
For n = 0, the equation (82) becomes
2 𝑑0 −𝑦2 (83)
𝐻0 (𝑦) = (−1)0 . 𝑒 𝑦 . .𝑒
𝑑𝑦 0
2 2
𝐻0 (𝑦) = 1. 𝑒 𝑦 . 1. 𝑒 −𝑦 = 𝑒 𝑦
2 −𝑦2
= 𝑒0 (84)
𝐻0 (𝑦) = 1 (85)
2 𝑑 −𝑦2 (86)
𝐻1 (𝑦) = (−1)1 . 𝑒 𝑦 . .𝑒
𝑑𝑦
2
𝐻1 (𝑦) = (−1). 𝑒 𝑦 . (−2𝑦). 𝑒 −𝑦
2
(87)
𝐻1 (𝑦) = (−1). (−2𝑦). 𝑒 𝑦

2 −𝑦 2
= 2𝑦. 𝑒 0 (88)
𝐻1 (𝑦) = 2𝑦 (89)
2 𝑑2 −𝑦2 (90)
𝐻2 (𝑦) = (−1)2 . 𝑒 𝑦 . .𝑒
𝑑𝑦 2
2 𝑑 2 (91)
𝐻2 (𝑦) = (+1). 𝑒 𝑦 . . −2𝑦. 𝑒 −𝑦
𝑑𝑦
2 2
𝐻2 (𝑦) = 𝑒 𝑦 [(−2𝑦)𝑒 −𝑦 (−2𝑦) + (−2)𝑒 −𝑦 ]
2
(92)
2
𝐻2 (𝑦) = 𝑒 𝑦 [(4𝑦 2 − 2)𝑒 −𝑦 ]
2
(93)
𝐻2 (𝑦) = (4𝑦 2 − 2)𝑒 𝑦

2 −𝑦 2
= (4𝑦 2 − 2)𝑒 0 (94)
𝐻2 (𝑦) = 4𝑦 2 − 2 (95)
The total wavefunction: After knowing the unknown part F(y), the complete eigenfunction for a simple
harmonic oscillator in the quantum mechanical world can be written as
𝜓𝑛 (𝑦) = 𝑁𝑛 𝐻𝑛 (𝑦) 𝑒 −𝑦
2 /2
(96)
Where 𝑁𝑛 is the normalization constant for nth state while the symbol 𝐻𝑛 (𝑦) represents the Hermit polynomial
of nth order in terms of y-variable. Once the wavefunctions are obtained in terms of y, they can easily be
converted into x-dependent function by simply putting 𝑦 = √𝛽𝑥.
no watermark.
Table 1. Eigenfunctions representing various quantum mechanical states of a simple harmonic oscillator.
α/β n Hn(y) ψn(y) ψn(x)
1 0 1 𝑁0 . 𝑒 −𝑦
2 /2
𝑁0 . 𝑒 −𝛽𝑥
2 /2
3 1 2𝑦 𝑁1 . 2𝑦. 𝑒 −𝑦
2 /2
𝑁1 (2√𝛽𝑥)𝑒 −𝛽𝑥
2 /2
5 2 4𝑦 2 − 2 𝑁2 (4𝑦 2 − 2)𝑒 −𝑦
2 /2
𝑁2 (4𝛽𝑥 2 − 2)𝑒 −𝛽𝑥
2 /2
7 3 8𝑦 3 − 12𝑦 𝑁3 (8𝑦 3 − 12𝑦)𝑒 −𝑦

2 /2
𝑁3 (8𝛽 3/2 𝑥 3 − 12√𝛽𝑥)𝑒 −𝛽𝑥
2 /2
The normalization constant can be obtained by recalling the fact that every wave function must describe the
corresponding state completely. This means that square of wave function under consideration over the whole
configurational space must be equal to unity i.e.
+∞ +∞ 2 (97)
𝛽𝑥 2
∫ 𝜓𝑛2 𝑑𝑥 = ∫ [𝑁𝑛 𝐻𝑛 (𝑥) 𝑒 − 2 ] =1
−∞ −∞
𝑁𝑛2 (98)
2𝑛 𝑛! √𝜋 = 1
√𝛽
√𝛽 (99)
𝑁𝑛2 =
2𝑛 𝑛! √𝜋
1/2 (100)
√𝛽
𝑁𝑛 = ( )
2𝑛 𝑛! √𝜋
It can be clearly seen from the above equation that the normalization consents are different for different states.
For instance, some of the normalization constants are given below.
1/2
𝛽 1/4 (101)
√𝛽
𝑁0 = ( ) =( )
20 0! √𝜋 𝜋
1/2
1 𝛽 1/4 (102)
√𝛽
𝑁1 = ( ) = ( )
21 1! √𝜋 √2 𝜋
1/2
1𝛽 1/4 (103)
√𝛽
𝑁2 = ( ) = ( )
22 2! √𝜋 2√2 𝜋
no watermark.
The eigenvalues of energy: Since we have already proved that the total wavefunction for a simple harmonic
oscillator is acceptable only when the following condition of equation (81) is satisfied i.e.
𝛼 (104)
= 2𝑛 + 1
𝛽
Furthermore, we also know that
8𝜋 2 𝑚𝐸 4𝜋 2 𝑚𝜈 (105)
𝛼= 𝑎𝑛𝑑 𝛽=
ℎ2 ℎ
After using the value of α and β, the equation (104) take the form
8𝜋 2 𝑚𝐸 ℎ (106)
2
× 2 = 2𝑛 + 1
ℎ 4𝜋 𝑚𝜈
or
4𝜋 2 𝑚𝜈 ℎ2 (107)
𝐸 = (2𝑛 + 1) × 2
ℎ 8𝜋 𝑚
or
ℎ𝜈 (108)
𝐸𝑛 = (2𝑛 + 1)
2
or
1 (109)
𝐸𝑛 = (𝑛 + ) ℎ𝜈
2
Where n is a discrete variable (vibrational quantum number) with values 0, 1, 2, 3…∞. The symbol En
represents the vibrational energies of different vibrational states.
 The Classical and Quantum-Mechanical Interpretation of Vibrational States
In order to have a relative interpretation of vibrational states in the classical and quantum-mechanical
framework, recall the classical expression for potential energy curve of simple harmonic oscillator i.e.
1 (110)
𝑉 = 𝑘𝑥 2
2
Where k is the force constant and x is the displacement induced. Also, the general expressions for all the
vibrational states and corresponding energies are
2 1 (111)
𝜓𝑛 (𝑥) = 𝑁𝑛 𝐻𝑛 (𝑥) 𝑒 −𝛽𝑥 𝑎𝑛𝑑 𝐸𝑛 = (𝑛 + ) ℎ𝜈
2
Where 𝑁𝑛 and 𝐻𝑛 (𝑥) are the normalization constant and Hermit polynomial for nth state.
no watermark.
Figure 4. The depiction of various vibrational states of a simple harmonic oscillator in the classical and
quantum mechanical framework.
After looking at the figure given above, the following points can be made about the differences and similarities
in the classical and quantum mechanical oscillators.
i) It can be clearly seen that the energy levels of a classical oscillator are continuous including zero while the
energy levels the quantum-mechanical analog is discontinuous with zero-point energy of hν/2. In other words,
the classical oscillator can have zero vibrational energy but the vibrational motion cannot be ceased completely
in case of the quantum mechanical version of the simple harmonic oscillator.
ii) There is always a limit over the compression as well as over the expansion in the classical oscillator to have
a certain amount of energy. On the other hand, since the function becomes zero only at infinite displacement,
there is no limit over the compression and expansion in the quantum oscillator theoretically.
no watermark.
iii) The classical oscillator spends more time in the extreme states i.e. fully compressed and fully expended,
and spends the least time with equilibrium bond length. As far as the ground vibrational state of the quantum
mechanical oscillator is concerned, it spends most time with equilibrium (because the function is maximum
for requ or x = 0), and probability to spend time in compressed and expended mode decreases as the magnitude
of compression and expansion increases.
iv) If we plot the square of wavefunction vs displacement incorporated, it can be clearly seen that the most
probable bond lengths shift towards the compressed and expanded states as the quantum number increases
which is in accordance with the Bohr’s correspondence principle.
Figure 5. The variation of probability as a function of bond length or displacement in different vibrational
states of a simple harmonic oscillator.
Furthermore, it also worthy to note that all 𝜓𝑒𝑣𝑒𝑛 states are symmetric while all 𝜓𝑜𝑑𝑑 wavefunctions are
asymmetric in nature with 𝑛 nodes.
no watermark.
 Zero Point Energy of a Particle Possessing Harmonic Motion and Its

Consequence
In order to understand the minimum or the zero-point energy of a simple harmonic oscillator, recall
the general wavefunction representing all the vibrational states of a simple harmonic oscillator i.e.
𝜓𝑛 (𝑦) = 𝑁𝑛 𝐻𝑛 (𝑦) 𝑒 −𝑦
2 /2
(112)
Where y is a displacement-based variable with a value equal to √𝛽x. The constant β depends upon the reduced
mass of the oscillator (m) and equilibrium vibrational frequency (ν) as
4𝜋 2 𝑚𝜈 (113)
𝛽=
ℎ
The symbol 𝑁𝑛 and 𝐻𝑛 (𝑦) are the normalization constant and Hermit polynomial for nth state i.e.
1/2
𝑑𝑛 (114)
√𝛽 𝑦2 2
𝑁𝑛 = ( ) 𝑎𝑛𝑑 𝐻𝑛 (𝑦) = (−1)𝑛 . 𝑒 . 𝑛 . 𝑒 −𝑦
2𝑛 𝑛! √𝜋 𝑑𝑦
Also, the general expression for the energies is given below.
1 (115)
𝐸𝑛 = (𝑛 + ) ℎ𝜈
2
Now, for the ground vibrational state (𝑛 = 0), 𝑁0 and 𝐻0 (𝑦) can be obtained from equation (114) i.e.
𝛽 1/4 (116)
𝑁0 = ( ) 𝑎𝑛𝑑 𝐻0 (𝑦) = 1
𝜋
After using the values of y, 𝑁0 and 𝐻0 (𝑦) in equation (112), the ground state function becomes
𝛽 1/4 2
(117)
𝜓0 (𝑥) = ( ) . 1. 𝑒 −𝛽𝑥 /2
𝜋
Hence, the ground state wave function does not collapse at 𝑛 = 0, which means that corresponding energy can
also be obtained by putting 𝑛 = 0 in equation (115) i.e.
1 (118)
𝐸0 = (0 + ) ℎ𝜈
2
or
1 (119)
𝐸0 = ℎ𝜈
2
The above equation gives the minimum energy which is always possessed by a simple harmonic oscillator.

Figure 6. The variation of ground vibrational wavefunction and probability as a function of bond length or
displacement in a simple harmonic oscillator.
It is well-known that the classical oscillator spends more time in the extreme states i.e. fully
compressed and fully expended, and spends the least time with equilibrium bond length. However, as far as
the ground vibrational state of the quantum mechanical oscillator is concerned, it spends the most time with
equilibrium (because the function is maximum for requ or x = 0), and probability to spend time in compressed
and expended mode decreases as the magnitude of compression and expansion increases. Moreover, there is
always a limit over the compression as well as over the expansion in the classical oscillator to have a certain
amount of energy; however, since the function becomes zero only at infinite displacement, there is no limit
over the compression and expansion in the quantum oscillator theoretically.
It is also worthy to note that the energy given by the equation (119) is in joules. However, in many
textbooks or papers, it is also reported in terms of wavenumbers. To do so, we need first put the value of
frequency as 𝜈 = 𝑐/𝜆 and then 1/𝜆 = 𝜈̅ in the equation (119) i.e.
1 𝑐 1 (119)
𝐸0 = ℎ = ℎ𝑐𝜈̅
2 𝜆 2
Where c is the velocity of light. Now, to convert the zero-point energy in wavenumbers, divide equation (119)
by ℎ𝑐 i.e.
1 ℎ𝑐𝜈̅ 𝜈̅ (120)
𝜈̅0 = =
2 ℎ𝑐 2
no watermark.
 Schrodinger Wave Equation for Three Dimensional Rigid Rotator

In order to study the rotational behavior of a diatomic molecule, consider a system two masses m1
and m2 joined by a rigid rod of length “r”. Now assume that this dumbbell type geometry rotates about an axis
that is perpendicular to r and passes through the center of mass.
Figure 7. The pictorial representation of the diatomic rigid rotator in classical mechanics.
If 𝑣1 and 𝑣2 are the velocities of the mass m1 and m2 revolving about the axis of rotation, the total kinetic
energy (T) of the rotator can be given by the following relation.
1 1 (121)
𝑇 = 𝑚1 𝑣12 + 𝑚2 𝑣22
2 2
Since we know that linear velocity 𝑣 is simply equal to the angular velocity 𝜔 multiplied by the radius of
rotation r i.e. 𝑣 = 𝜔𝑟, the equation (121) takes the form
1 1 (122)
𝑇 = 𝑚1 (𝑟1 𝜔)2 + 𝑚2 (𝑟2 𝜔)2
2 2
1 (123)
𝑇 = (𝑚1 𝑟12 + 𝑚2 𝑟22 )𝜔2
2
1 (123)
𝑇 = 𝐼𝜔2
2
Where I is the moment of inertia with definition 𝐼 = ∑ 𝑚𝑖 𝑟𝑖2 . Furthermore, we know from mass-center that

𝑚1 𝑟1 = 𝑚2 𝑟2 (124)
Now since 𝑟 = 𝑟1 + 𝑟2 , we rearrange equation (124) to give

𝑚2 𝑚1 (125)
𝑟1 = 𝑟 𝑎𝑛𝑑 𝑟2 = 𝑟
𝑚1 + 𝑚2 𝑚1 + 𝑚2
In the two-mass system 𝐼 = 𝑚1 𝑟12 + 𝑚2 𝑟22 , so have
𝑚2 2 𝑚1 2 (126)
𝐼 = 𝑚1 ( 𝑟) + 𝑚2 ( 𝑟)
𝑚1 + 𝑚2 𝑚1 + 𝑚2
𝑚1 𝑚2 (127)
𝐼=( ) 𝑟2
𝑚1 + 𝑚2
𝐼 = 𝜇𝑟 2 (128)
Where 𝜇 = 𝑚1 𝑚2 /𝑚1 + 𝑚2 is the reduced mass of the rigid diatomic system. Since we that the kinetic energy
and linear moment of a particle of mass m moving with velocity v are
1 (129)
𝑇 = 𝑚𝑣 2 𝑎𝑛𝑑 𝑝 = 𝑚𝑣
2
The counterparts in the angular motion can be written as
1 (130)
𝑇 = 𝐼𝜔2 𝑎𝑛𝑑 𝐿 = 𝐼𝜔
2
Multiplying and dividing the rotational kinetic energy by I, we have
𝐼 2 𝜔2 (𝐼𝜔)2 𝐿2 (131)
𝑇= = =
2𝐼 2𝐼 2𝐼
It is clear from the above equation that the kinetic energy of a classical rotator can have any value because the
value-domain of angular velocity is continuous. Moreover, as no external force is working on the rotator, the
potential can be set to zero. In other words, the Hamiltonian for diatomic rigid rotator can be given as
̂ = 𝑇̂ + 𝑉̂
𝐻 (132)
𝐿̂2 (133)
̂=
𝐻 +0
2𝐼
The expression for the operator 𝐿̂2 in polar coordinates is
ℎ2 1 𝜕 𝜕 1 𝜕 (134)
𝐿2 = − 2 [ (𝑆𝑖𝑛 𝜃 ) + 2 ]
4𝜋 𝑆𝑖𝑛 𝜃 𝜕𝜃 𝜕𝜃 𝑆𝑖𝑛 𝜃 𝜕𝜙
Using equation (134) in equation (133), the Hamiltonian operator takes the form
no watermark.
ℎ2 1 𝜕 𝜕 1 𝜕 (135)
̂=−
𝐻 [ (𝑆𝑖𝑛 𝜃 ) + ]+0
8𝜋 2 𝐼 𝑆𝑖𝑛 𝜃 𝜕𝜃 𝜕𝜃 𝑆𝑖𝑛2 𝜃 𝜕𝜙
Now, let ψ be the function that describes all the rotational states of the diatomic rigid rotator. The operation of
Hamiltonian operator over ψ can be rearranged to give to construct the Schrodinger wave equation; and we all
know that the wave function as well the energy, both are the obtained as this second-order differential equation
is solved. Mathematically, we can say that
̂ 𝜓 = 𝐸𝜓
𝐻 (136)
After putting the expression of the Hamiltonian operator from equation (135) in equation (136), we get
ℎ2 1 𝜕 𝜕 1 𝜕 (137)
− 2 [ (𝑆𝑖𝑛 𝜃 ) + ] 𝜓 = 𝐸𝜓
8𝜋 𝐼 𝑆𝑖𝑛 𝜃 𝜕𝜃 𝜕𝜃 𝑆𝑖𝑛2 𝜃 𝜕𝜙
or
ℎ2 1 𝜕 𝜕𝜓 1 𝜕𝜓 (138)
− 2 [ (𝑆𝑖𝑛 𝜃 ) + ] = 𝐸𝜓
8𝜋 𝐼 𝑆𝑖𝑛 𝜃 𝜕𝜃 𝜕𝜃 𝑆𝑖𝑛2 𝜃 𝜕𝜙
or
1 𝜕 𝜕𝜓 1 𝜕𝜓 8𝜋 2 𝐼𝐸𝜓 (139)
(𝑆𝑖𝑛 𝜃 ) + = −
𝑆𝑖𝑛 𝜃 𝜕𝜃 𝜕𝜃 𝑆𝑖𝑛2 𝜃 𝜕𝜙 ℎ2
or
1 𝜕 𝜕𝜓 1 𝜕𝜓 8𝜋 2 𝐼𝐸𝜓 (140)
(𝑆𝑖𝑛 𝜃 ) + + =0
The above differential equation contains two variable 𝜙 and 𝜃, and therefore, is difficult to solve. Thus, we
need to use the same mathematical technique we used to study particle in a 3-dimensional box i.e. the
separation of variables. To do so, consider the total wavefunction as the product of two independent, one θ-
dependent and other as a ϕ-dependent function only i.e.
𝜓(𝜃, 𝜙) = 𝜓(𝜃) × 𝜓(𝜙) = 𝛩 × 𝛷 (141)
After putting the value of equation (141) in equation (140), we get
1 𝜕 𝜕𝛩𝛷 1 𝜕𝛩𝛷 8𝜋 2 𝐼𝐸𝛩𝛷 (142)

(𝑆𝑖𝑛 𝜃 )+ + =0
Since the first and second terms contain the partial derivatives w.r.t. θ and ϕ, respectively; function Φ and Θ
must be kept constant correspondingly, i.e.,
no watermark.
1 𝜕 𝜕𝛩 1 𝜕𝛷 8𝜋 2 𝐼𝐸𝛩𝛷 (143)
𝛷 (𝑆𝑖𝑛 𝜃 ) + 𝛩 + =0
Dividing the above equation by 𝛩𝛷, the equation (143) takes the form
1 1 𝜕 𝜕𝛩 1 1 𝜕𝛷 8𝜋 2 𝐼𝐸 (144)
(𝑆𝑖𝑛 𝜃 ) + + =0
𝛩 𝑆𝑖𝑛 𝜃 𝜕𝜃 𝜕𝜃 𝛷 𝑆𝑖𝑛2 𝜃 𝜕𝜙 ℎ2
After multiplying equation (144) by 𝑆𝑖𝑛2 𝜃, we get
𝑆𝑖𝑛 𝜃 𝜕 𝜕𝛩 1 𝜕𝛷 8𝜋 2 𝐼𝐸 (145)
(𝑆𝑖𝑛 𝜃 ) + + 𝑆𝑖𝑛2 𝜃 = 0
𝛩 𝜕𝜃 𝜕𝜃 𝛷 𝜕𝜙 ℎ2
Rearranging
𝑆𝑖𝑛 𝜃 𝜕 𝜕𝛩 8𝜋 2 𝐼𝐸 2
1 𝜕𝛷 (146)
(𝑆𝑖𝑛 𝜃 ) + 𝑆𝑖𝑛 𝜃 = −
𝛩 𝜕𝜃 𝜕𝜃 ℎ2 𝛷 𝜕𝜙
At this point, we can set both sides equal to constant m2 i.e.
𝑆𝑖𝑛 𝜃 𝜕 𝜕𝛩 8𝜋 2 𝐼𝐸 2 2
1 𝜕𝛷 (147)
(𝑆𝑖𝑛 𝜃 ) + 𝑆𝑖𝑛 𝜃 = 𝑚 = −
𝛩 𝜕𝜃 𝜕𝜃 ℎ2 𝛷 𝜕𝜙
The equation (147) can be fragmented into two equations, each containing a single variable i.e.
𝜕𝛷 (148)
+ 𝑚2 𝛷 = 0
𝜕𝜙
And
𝜕 𝜕𝛩 8𝜋 2 𝐼𝐸 (149)
𝑆𝑖𝑛 𝜃 (𝑆𝑖𝑛 𝜃 ) + 𝛩 𝑆𝑖𝑛2 𝜃 − 𝑚2 𝛩 = 0
𝜕𝜃 𝜕𝜃 ℎ2
Now dividing the above equation by 𝑆𝑖𝑛2 𝜃, we get
1 𝜕 𝜕𝛩 8𝜋 2 𝐼𝐸 𝑚2 𝛩 (150)
(𝑆𝑖𝑛 𝜃 ) + 𝛩 − =0
𝑆𝑖𝑛 𝜃 𝜕𝜃 𝜕𝜃 ℎ2 𝑆𝑖𝑛2 𝜃
or
1 𝜕 𝜕𝛩 8𝜋 2 𝐼𝐸 𝑚2 (151)
(𝑆𝑖𝑛 𝜃 ) + ( 2 − )𝛩 = 0
𝑆𝑖𝑛 𝜃 𝜕𝜃 𝜕𝜃 ℎ 𝑆𝑖𝑛2 𝜃
or
1 𝜕 𝜕𝛩 𝑚2 (152)
(𝑆𝑖𝑛 𝜃 ) + (𝛽 − )𝛩 = 0
𝑆𝑖𝑛 𝜃 𝜕𝜃 𝜕𝜃 𝑆𝑖𝑛2 𝜃
no watermark.
Where the constant β is defined as
8𝜋 2 𝐼𝐸 (153)
𝛽=
ℎ2
The solution of Φ equation: Recall the differential equation obtained after separation of variables having ϕ
dependence i.e.
𝜕𝛷 (154)
+ 𝑚2 𝛷 = 0
𝜕𝜙
The general solution of such an equation is
𝛷(𝜙) = 𝑁𝑒 𝑖𝑚𝜙 (155)
Where N represents the normalization constant. The wavefunction given above will be acceptable only if m
has integer value i.e. 0, ±1, ±2, etc. This can be understood in terms of single-valued, continuous and finite
nature of quantum states.
i) The boundary condition for function Φ: If we replace the angle “ϕ” with “ϕ + 2π”, the position of the point
under consideration should remain the same i.e.
𝛷(𝜙 + 2𝜋) = 𝛷(𝜙) (156)
Therefore
𝑁𝑒 𝑖𝑚(𝜙+2𝜋) = 𝑁𝑒 𝑖𝑚𝜙 (157)
or
𝑒 𝑖𝑚(𝜙+2𝜋) = 𝑒 𝑖𝑚𝜙 (158)
𝑒 𝑖𝑚𝜙 . 𝑒 𝑖𝑚2𝜋 = 𝑒 𝑖𝑚𝜙 (159)
𝑒 𝑖𝑚2𝜋 = 𝑒 𝑖𝑚𝜙 𝑒 −𝑖𝑚𝜙 (160)
𝑒 𝑖𝑚2𝜋 = 𝑒 𝑖𝑚𝜙−𝑖𝑚𝜙 = 𝑒 0 (161)
𝑒 𝑖𝑚2𝜋 = 1 (162)
Since we know from the Euler’s expansion 𝑒 𝑖𝑥 = 𝐶𝑜𝑠 𝑥 + 𝑖 𝑆𝑖𝑛 𝑥, the equation (162) takes the form
𝑒 𝑖𝑚2𝜋 = 𝐶𝑜𝑠 2𝜋𝑚 + 𝑖 𝑆𝑖𝑛 2𝜋𝑚 (163)
𝐶𝑜𝑠 2𝜋𝑚 + 𝑖 𝑆𝑖𝑛 2𝜋𝑚 = 1 (164)
The relation holds true only when we use 𝑚 = 0, ±1, ±2, ±3, ±4, etc.
no watermark.
ii) The normalization constant for function Φ: In order to determine the normalization constant for the Φ
function, we must put the squared-integral over whole configuration space as unity i.e.
2𝜋 (165)
∗
∫ 𝛷 𝛷 𝑑𝜙 = 1
0
or
2𝜋 (166)
2 𝑖𝑚𝜙 −𝑖𝑚𝜙
𝑁 ∫ 𝑒 .𝑒 𝑑𝜙 = 1
0
2𝜋 2𝜋 (167)
2 𝑖𝑚𝜙−𝑖𝑚𝜙
𝑁 ∫ 𝑒 𝑑𝜙 = 𝑁 ∫ 𝑒 0 𝑑𝜙 = 1
2
0 0
𝑁 2 [𝜙]2𝜋 2
0 = 𝑁 [2𝜋] = 1 (168)
(169)
1
𝑁=√
2𝜋
After using the value of normalization constant in equation (155), we get
(170)
1
𝛷(𝜙) = √ 𝑒 ±𝑖𝑚𝜙
2𝜋
Solution of Θ equation: Recall the differential equation obtained after separation of variables having θ
dependence i.e.
1 𝜕 𝜕𝛩 𝑚2 (171)
(𝑆𝑖𝑛 𝜃 ) + (𝛽 − )𝛩 = 0
After defining a new variable 𝑥 = 𝐶𝑜𝑠 𝜃, we have
𝑆𝑖𝑛2 𝜃 + 𝐶𝑜𝑠 2 𝜃 = 1 (172)
𝑆𝑖𝑛2 𝜃 = 1 − 𝐶𝑜𝑠 2 𝜃 (173)
𝑆𝑖𝑛 𝜃 = √1 − 𝐶𝑜𝑠 2 𝜃 (174)
𝑆𝑖𝑛 𝜃 = √1 − 𝑥 2 (175)
Also, since we assumed 𝑥 = 𝐶𝑜𝑠 𝜃, the first derivative w.r.t. θ will be
no watermark.
𝜕𝑥 (176)
= −𝑆𝑖𝑛 𝜃
𝜕𝜃
The derivative of Θ function w.r.t. θ can be rewritten as
𝜕𝛩 𝜕𝛩 𝜕𝑥 (177)
= .
𝜕𝜃 𝜕𝑥 𝜕𝜃
After putting the values of 𝜕𝑥/𝜕𝜃 from equation (176) in equation (177), we get
𝜕𝛩 𝜕𝛩 (178)
𝜕𝜃 𝜕𝑥
After removing Θ from both sides
𝜕 𝜕 (179)
𝜕𝜃 𝜕𝑥
Multiplying both sides of equation (178) by 𝑆𝑖𝑛 𝜃, we have
𝜕𝛩 𝜕𝛩 (180)
𝑆𝑖𝑛 𝜃 = −𝑆𝑖𝑛2 𝜃
𝜕𝜃 𝜕𝑥
𝜕𝛩 𝜕𝛩 (181)
𝑆𝑖𝑛 𝜃 = −(1 − 𝑥 2 )
𝜕𝜃 𝜕𝑥
Now, after putting the values of equation (179) and (181) in equation (171), we get
1 𝜕 𝜕𝛩 𝑚2 (182)
(−𝑆𝑖𝑛 𝜃 ) [−(1 − 𝑥 2 ) ] + (𝛽 − )𝛩 = 0
𝑆𝑖𝑛 𝜃 𝜕𝑥 𝜕𝑥 1 − 𝑥2
or
𝜕 𝜕𝛩 𝑚2 (183)
[(1 − 𝑥 2 ) ] + (𝛽 − )𝛩 = 0
𝜕𝑥 𝜕𝑥 1 − 𝑥2
The equation given above is a Legendre’s polynomial and has physical significance only in the range of 𝑥 =
+1 to − 1. Therefore, consider that one more form of Θ function so that this condition is satisfied i.e.
𝑚
𝛩(𝜃) = (1 − 𝑥 2 ) 2 . 𝑋(𝑥) (184)
Where X is a function depending upon variable x. The differentiation of the above equation w.r.t. x yields
𝜕𝛩 𝑚 𝑚 𝑑𝑋 (185)
= −𝑚𝑥(1 − 𝑥 2 ) 2 −1 . 𝑋 + (1 − 𝑥 2 ) 2 .
𝜕𝑥 𝑑𝑥
After multiplying the above equation by 1 − 𝑥 2 and 𝜕/𝜕𝑥, we get
no watermark.
𝜕 𝜕𝛩 𝜕 𝑚 𝑚 𝑑𝑋 (186)
[(1 − 𝑥 2 ) ] = [−𝑚𝑥(1 − 𝑥 2 ) 2 . 𝑋 + (1 − 𝑥 2 ) 2 +1 . ]
𝜕𝑥 𝜕𝑥 𝜕𝑥 𝑑𝑥
𝑚 𝑚
= [−𝑚(1 − 𝑥 2 )𝑚/2 + 𝑚2 𝑥 2 (1 − 𝑥 2 ) 2 −1 ] 𝑋 − [2𝑥(𝑚 + 1)(1 − 𝑥 2 ) 2 ] 𝑋 ′ (187)
𝑚
+ [(1 − 𝑥 2 ) 2 +1 ] 𝑋 ′′
Where 𝜕/𝜕𝑥 and 𝜕 2 /𝜕𝑥 2 are represented by the symbol 𝑋 ′ and 𝑋 ” , respectively. Now, after using the value of
equation (184) and equation (187) in equation (183), we get
−1
𝑚 𝑚
(188)
[−𝑚(1 − 𝑥 2 )𝑚/2 + 𝑚2 𝑥 2 (1 − 𝑥 2 ) 2 ] 𝑋 − [2𝑥(𝑚 + 1)(1 − 𝑥 2 ) 2 ] 𝑋 ′
𝑚 𝑚2 𝑚
+ [(1 − 𝑥 2 ) 2 +1 ] 𝑋 ′′ + (𝛽 − 2 ) (1 − 𝑥 2 ) 2 . 𝑋 = 0
1−𝑥
Dividing above expression by (1 − 𝑥 2 )𝑚/2 , we have
(1 − 𝑥 2 )𝑋 ′′ − 2(𝑚 + 1)𝑥𝑋 ′ + [𝛽 − 𝑚(𝑚 + 1)]𝑋 = 0 (189)
or
(1 − 𝑥 2 )𝑋 ′′ − 2𝛼𝑥𝑋 ′ + 𝜆𝑋 = 0 (190)
Where 𝛼 = 𝑚 + 1 and 𝜆 = 𝛽 − 𝑚(𝑚 + 1). Now assume that the function X can be expressed as a power
series expansion as given below.
𝑋 = 𝑎0 + 𝑎1 𝑥 + 𝑎2 𝑥 2 + 𝑎3 𝑥 3 … … … … (191)
𝑋 ′ = 𝑎1 + 2𝑎2 𝑥 + 3𝑎3 𝑥 2 … … … … (192)
𝑋 ′′ = 2𝑎2 + 6𝑎3 𝑥 + 12𝑎4 𝑥 2 … … … … (193)
Putting values of equation (191-193) in equation (190), we get
(1 − 𝑥 2 )(2𝑎2 + 6𝑎3 𝑥 + 12𝑎4 𝑥 2 + 20𝑎5 𝑥 3 ) − 2𝛼𝑥(𝑎1 + 2𝑎2 𝑥 + 3𝑎3 𝑥 2 + 4𝑎4 𝑥 3 ) (194)

+ 𝜆(𝑎0 + 𝑎1 𝑥 + 𝑎2 𝑥 2 + 𝑎3 𝑥 3 ) = 0
or
(2𝑎2 + 𝜆𝑎0 ) + [6𝑎3 + (𝜆 − 2𝛼)𝑎1 ]𝑥 + [12𝑎4 + (𝜆 − 2𝛼 − 2)𝑎2 ]𝑥 2 … … … = 0 (195)
The above equation is satisfied only if each term on the left-hand side is individually equal to zero i.e.
coefficients of each power of x are vanish. The general expression for the coefficients must follow the condition
given below.
(𝑛 + 1)(𝑛 + 2)𝑎𝑛+2 + [𝜆 − 2𝑛𝛼 − 𝑛(𝑛 − 1)]𝑎𝑛 = 0 (196)
no watermark.
Where 𝑛 = 0, 1, 2, 3 etc. Summarizing the result, we can write
2𝑛𝛼 + 𝑛(𝑛 − 1) − 𝜆 (197)

𝑎𝑛+2 = 𝑎𝑛
(𝑛 + 1)(𝑛 + 2)
After putting values of α and λ in equation (197), we get
𝑎𝑛+2 (𝑛 + 𝑚)(𝑛 + 𝑚 + 1) − 𝛽 (198)

=
𝑎𝑛 (𝑛 + 1)(𝑛 + 2)
Which is the Recursion formula for the coefficients of the power of x. Now, in order to obtain a valid
wavefunction, the power series must contain a finite number of terms which is possible only if numerator
becomes zero i.e.
(𝑛 + 𝑚)(𝑛 + 𝑚 + 1) − 𝛽 = 0 (199)
𝛽 = (𝑛 + 𝑚)(𝑛 + 𝑚 + 1) (200)
Since we know that m as well n both are the whole numbers, their sum must also be a whole number. Therefore,
the sum of n and m can be replaced by another whole number symbolized by l i.e.
𝛽 = 𝑙(𝑙 + 1) (201)
Where 𝑙 = 0, 1, 2, 3 etc. After putting the value of β from equation (201) in equation (183), we get
𝜕 𝜕𝛩 𝑚2 (202)
[(1 − 𝑥 2 ) ] + [𝑙(𝑙 + 1) − ]𝛩 = 0
𝜕𝑥 𝜕𝑥 1 − 𝑥2
The general solution of equation (202) is
𝛩 = 𝑁𝑃𝑙𝑚 (𝑥) = 𝑁𝑃𝑙𝑚 (𝐶𝑜𝑠 𝜃) (203)
Where N is the normalization constant and 𝑃𝑙𝑚 (𝑥) is the associated “Legendre function” which is defined as
given below.
𝑑𝑚 𝑃𝑙 (𝑥) (204)
𝑃𝑙𝑚 (𝑥) = (1 − 𝑥 2 )𝑚/2
𝑑𝑥 𝑚
Where 𝑃𝑙 (𝑥) is the Legendre polynomial given by
1 𝑑𝑙 (𝑥 2 − 1)𝑙 (205)
𝑃𝑙 (𝑥) =
2𝑙 𝑙! 𝑑𝑥 𝑙
In order to proceed further, we must discuss the concept of orthogonality and the normalization of the
“Legendre’s function”.
i) Orthogonality of associated Legendre’s function: The orthogonality of the associated Legendre’s polynomial
follows the conditions given below.
no watermark.
+1 (206)
∫ 𝑃𝑘𝑚 (𝑥) 𝑃𝑙𝑚 (𝑥) =0 𝑖𝑓 𝑘 ≠ 𝑙
−1
+1 (207)
2 (𝑙 + 𝑚)!
∫ 𝑃𝑘𝑚 (𝑥) 𝑃𝑙𝑚 (𝑥) = 𝑖𝑓 𝑘 = 𝑙
(2𝑙 + 1) (𝑙 − 𝑚)!
−1
ii) Normalization of associated Legendre’s function: The normalization of the associated Legendre’s
polynomial follows the conditions given below.
+1 (208)
∗
∫ 𝛩𝑚,𝑙 𝛩𝑚,𝑙 (𝑑𝜃) = 1
−1
+1 (209)
2
𝑁 ∫ 𝑃𝑘𝑚 (𝑥) 𝑃𝑙𝑚 (𝑥) 𝑑𝑥 =1
−1
After solving the integral, we get
2 (𝑙 + 𝑚)! (210)
𝑁2. =1
(2𝑙 + 1) (𝑙 − 𝑚)!
(211)
(2𝑙 + 1)(𝑙 − 𝑚)!
𝑁=√
2(𝑙 + 𝑚)!
Using the value of normalization constant in equation (203), we get
(212)
(2𝑙 + 1)(𝑙 − 𝑚)! 𝑚
𝛩(𝜃) = √ . 𝑃𝑙 (𝐶𝑜𝑠 𝜃)
2(𝑙 + 𝑚)!
The complete eigenfunction of rigid rotator: The total eigenfunction for the rigid rotator now can be
obtained by simply multiplying the solution of ϕ-dependent and θ-dependent differential equations i.e.
equation (170) and equation (203).
(213)
(2𝑙 + 1)(𝑙 − 𝑚)! 𝑚 1
𝜓𝑙,𝑚 (𝜃, 𝜙) = 𝛩𝑙,𝑚 (𝜃)𝛷𝑚 (𝜙) = √ . 𝑃𝑙 (𝐶𝑜𝑠 𝜃). √ 𝑒 ±𝑖𝑚𝜙
2(𝑙 + 𝑚)! 2𝜋
(214)
1 (2𝑙 + 1)(𝑙 − 𝑚)! 𝑚
𝜓𝑙,𝑚 (𝜃, 𝜙) = √ √ . 𝑃𝑙 (𝐶𝑜𝑠 𝜃). 𝑒 ±𝑖𝑚𝜙
2𝜋 2(𝑙 + 𝑚)!
no watermark.
 Energy of Rigid Rotator

The energy of a rigid rotator can be understood only after considering its classical and quantum
mechanical aspects. In the previous section of this chapter, we discussed the classical and quantum mechanical
nature of the rigid rotator. consider a system two masses m1 and m2 joined by a rigid rod of length “r”. Now
assume that this dumbbell type geometry rotates about an axis that is perpendicular to r and passes through the
center of mass.
 The energy of Classical Rigid Rotator
If 𝑣1 and 𝑣2 are the velocities of the mass m1 and m2 revolving about the axis of rotation, the total
kinetic energy (T) of the rotator can be given by the following relation.
1 1 (215)
𝑇 = 𝑚1 𝑣12 + 𝑚2 𝑣22
2 2
Since we know that linear velocity 𝑣 is simply equal to the angular velocity 𝜔 multiplied by the radius of
rotation r i.e. 𝑣 = 𝜔𝑟, the equation (215) takes the form
1 1 (216)
𝑇 = 𝑚1 (𝑟1 𝜔)2 + 𝑚2 (𝑟2 𝜔)2
2 2
1 (217)
𝑇 = (𝑚1 𝑟12 + 𝑚2 𝑟22 )𝜔2
2
1 (218)
𝑇 = 𝐼𝜔2
2
Where I is the moment of inertia equal with definition 𝐼 = ∑ 𝑚𝑖 𝑟𝑖2 . Furthermore, the value of I can also be
written as
𝑚1 𝑚2 (219)
𝐼=( ) 𝑟2
𝑚1 + 𝑚2
𝐼 = 𝜇𝑟 2 (220)
Where 𝜇 = 𝑚1 𝑚2 /𝑚1 + 𝑚2 is the reduced mass of the rigid diatomic system. After multiplying and dividing
the rotational kinetic energy by I i.e. equation (218), we have
𝐼 2 𝜔2 (𝐼𝜔)2 𝐿2 (221)
𝑇= = =
2𝐼 2𝐼 2𝐼
Where L is the angular momentum of the rotator. It is clear from the above equation that the kinetic energy of
a classical rotator can have any value because the value-domain of angular velocity is continuous. Moreover,
as now the external force is working on the rotator, the potential can be set to zero. Therefore, we can conclude
that the total energy of a classical diatomic rigid rotator is given by equation (221).

 The energy of Quantum Mechanical Rigid Rotator

In order to understand the energy of a quantum mechanical rigid rotator, recall the Schrodinger wave
equation for the same first i.e.
1 𝜕 𝜕𝜓 1 𝜕𝜓 8𝜋 2 𝐼𝐸𝜓 (222)
(𝑆𝑖𝑛 𝜃 ) + + =0
Where ψ is the mathematical expression defining various quantum mechanical states depending upon two
variables θ and ϕ. During the course of the solution of the above equation, a constant β is defined for simplicity
as given below.
8𝜋 2 𝐼𝐸 (223)
𝛽=
ℎ2
However, the boundary conditions that keep the function single-valued, continuous and finite; also proved that
the constant β must satisfy the following condition also.
𝛽 = 𝑙(𝑙 + 1) (224)
Where 𝑙 = 0, 1, 2, 3, 4 etc. After equating the value of β from equation (223) and equation (224), we get
8𝜋 2 𝐼𝐸 (225)
= 𝑙(𝑙 + 1)
ℎ2
ℎ2 (226)
𝐸𝑙 = 2 𝑙(𝑙 + 1)
8𝜋 𝐼
Hence, unlike the classical counterpart, the energy levels of quantum mechanical rigid rotators are
discontinuous.
Figure 8. The energy level diagram of the diatomic rigid rotator in units of ℎ2 /8𝜋 2 𝐼.
no watermark.
 Space Quantization
The solution of the Schrodinger wave equation for the diatomic rigid rotator provided the
mathematical descriptions of all the rotational states along with their corresponding energies. The general form
of total eigenfunction for the rigid rotator is given below.
(227)
1 (2𝑙 + 1)(𝑙 − 𝑚)! 𝑚
𝜓𝑙,𝑚 (𝜃, 𝜙) = √ √ . 𝑃𝑙 (𝐶𝑜𝑠 𝜃). 𝑒 ±𝑖𝑚𝜙
2𝜋 2(𝑙 + 𝑚)!
Where ψ is the mathematical expression defining various quantum mechanical states depending upon two
variables θ and ϕ. Furthermore, the most important property of a rigid rotator after energy is the angular
momentum which can be obtained using the last postulate of quantum mechanics i.e.
(228)
< 𝐿 >= ∮ 𝜓𝑙,𝑚 (𝜃, 𝜙) 𝐿̂ 𝜓𝑙,𝑚 (𝜃, 𝜙)
ℎ (229)
𝐿𝑙 = √𝑙(𝑙 + 1)
2𝜋
Alternatively, we know that the energies of various rotational states of rigid rotators are given by the following
relation.
ℎ2 (230)
𝐸= 𝑙(𝑙 + 1)
8𝜋 2 𝐼
Where 𝑙 = 0, 1, 2, 3, 4 etc. Also, we know that the angular momentum and energy are related classically as
1 (𝐼𝜔)2 𝐿2 (231)
𝐸= 𝐼𝜔2 = =
2 2𝐼 2𝐼
or
𝐿 = √2𝐸𝐼 (232)
After using the value of energy from equation (230) into equation (232), we get
(233)
ℎ2
𝐿𝑙 = √2𝐼. 𝑙(𝑙 + 1)
8𝜋 2 𝐼
or
(234)
ℎ2
𝐿𝑙 = √ 2 𝑙(𝑙 + 1)
4𝜋
or

ℎ (235)
𝐿𝑙 = √𝑙(𝑙 + 1)
2𝜋
Which is exactly the same as given by equation (229). Since 𝑙 = 0, 1, 2, 3, 4 etc., the quantum mechanically
allowed values of angular momentum (in the units of ℎ/2𝜋) are given below.
𝐿0 = √0(0 + 1) unit = 0 unit (236)
𝐿1 = √1(1 + 1) unit = √2 unit (237)
𝐿2 = √2(2 + 1) unit = √6 unit (238)
𝐿3 = √3(3 + 1) unit = √12 unit (239)
However, there is boundary condition in quantum mechanics that says that only integral effects are allowed
reference direction if the angular momentum is generated by integral quantum number and half-integral effects
are allowed in reference direction if the momentum is generated by half-integral quantum number.
This can be understood by taking the example of a diatomic molecule rotating in the first excited
rotational state i.e. 𝑙 = 1. The angular momentum of such a molecule will be √2 or 1.414 units. However,
since this angular momentum is obtained using an integral quantum number (𝑙 = 1), only integral effects (i.e.
+1, 0, −1) are allowed in reference direction. Now if z-axis is the reference direction, the effect of any vector
𝐴 in the reference direction is calculated by multiplying its magnitude with the cosine of the angle it makes
with reference direction.
Figure 9. The angular momentum of the diatomic rigid rotator (left) and its rectangular resolution.
no watermark.
In tringle OPC, the side OC represents the effect of the angular momentum vector 𝐴 along z-axis, can be
calculated as given below.
𝑂𝐶 (240)
= 𝐶𝑜𝑠 𝜃
𝑂𝑃
𝑂𝐶 = 𝑂𝑃. 𝐶𝑜𝑠 𝜃 (241)
𝐴𝑧 = 𝐴 𝐶𝑜𝑠 𝜃 (242)
Hence, a diatomic molecule in its first rotational state cannot rotate in xy-plane since it will generate √2 or
1.414 units of angular momentum along the z-axis (from right-hand thumb rule). In other words, the √2 units
of angular momentum cannot orient itself along z-axis because this makes 𝜃 = 0° and since 𝐶𝑜𝑠 0 = 1, 𝐴𝑧 =
𝐴 i.e. angular momentum effect along the z-axis is also 1.414 unit which is not allowed quantum mechanically.
The effects of angular momentum allowed in the z-direction are +1, 0, −1; for which angles required are
determined as follows.
1 (243)
+1 = √2 𝐶𝑜𝑠 𝜃 ⇒ 𝜃 = 𝐶𝑜𝑠 −1 = 45°
√2
0 (244)
0 = √2 𝐶𝑜𝑠 𝜃 ⇒ 𝜃 = 𝐶𝑜𝑠 −1 = 90°
√2
−1 (245)
−1 = √2 𝐶𝑜𝑠 𝜃 ⇒ 𝜃 = 𝐶𝑜𝑠 −1 = 135°
√2
Hence, we can say that in order to be allowed, the 1.414 units of angular momentum must orient itself only at
45°, 90° and 135° in space from reference direction (z-axis in this case).
Figure 10. The space quantization of angular momentum of rigid rotator in l = 1 rotational state.
no watermark.
Since the orientation of angular momentum can orient itself in any direction from the z-axis as far as the
effective angular momentum +1 unit along z-direction; therefore, we should use a cone around the same at
45°. The same is true for 0 and −1 effects with 90° and 135°, respectively.
Figure 11. The space quantization of angular momentum of the rigid rotator in l = 0, 1, 2 and 3 states.
It is also worthy to mention that the concept of space quantization is equally applicable to the angular
momentums of all other systems also like orbital or spin angular momentum of electrons or nuclei.
no watermark.
 Schrodinger Wave Equation for Hydrogen Atom: Separation of Variable in

Polar Spherical Coordinates and Its Solution
In the first section of this chapter, we derived and discussed the Schrodinger wave equation for a
particle in a three-dimensional box. In this section, we will apply the procedure to an electron that exits around
the nucleus. In order to do so, consider an electron at a distance r from the center of the nucleus, and this
electron can travel in any direction i.e. along x-, y- and z-axis. The potential energy of such an electron-nucleus
system will be −𝑍𝑒 2 /𝑟; where 𝑍𝑒 and 𝑒 are charges on nucleus and electron respectively.
Figure 12. An electron around nucleus at r distance.
So far we have considered a quantum mechanical system of an electron around the nucleus. Now suppose that
we need to find various physical properties associated with different states of this system. Had it been a
classical system, we would use simple formulas from classical mechanics to determine the value of different
physical properties. However, being a quantum mechanical system, we cannot use those expressions because
they would give irrational results. Therefore, we need to use the postulates of quantum mechanics to evaluate
various physical properties.
Let ψ be the function that describes all the states of the electron around the nucleus. At this point we
have no information about the exact mathematical expression of ψ; nevertheless, we know that there is one
operator that does not need the absolute expression of wave function but uses the symbolic form only, the
Hamiltonian operator. The operation of Hamiltonian operator over this symbolic form can be rearranged to
give to construct the Schrodinger wave equation; and we all know that the wave function as well the energy,
both are the obtained as this second-order differential equation is solved. Mathematically, we can say that
̂ 𝜓 = 𝐸𝜓
𝐻 (246)
After putting the value of three-dimensional Hamiltonian in equation (1), we get
−ℎ2 𝜕 2 𝜕2 𝜕2 (247)
[ 2 ( 2 + 2 + 2 ) + 𝑉] 𝜓 = 𝐸𝜓
8𝜋 𝑚 𝜕𝑥 𝜕𝑦 𝜕𝑧
or

−ℎ2 𝜕 2 𝜓 𝜕 2 𝜓 𝜕 2 𝜓 (248)
( + + ) + 𝑉𝜓 = 𝐸𝜓
8𝜋 2 𝑚 𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2
−ℎ2 𝜕 2 𝜓 𝜕 2 𝜓 𝜕 2 𝜓 (249)
( + + ) + 𝑉𝜓 − 𝐸𝜓 = 0
8𝜋 2 𝑚 𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2
𝜕 2 𝜓 𝜕 2 𝜓 𝜕 2 𝜓 8𝜋 2 𝑚 (250)
+ + + (𝐸 − 𝑉)𝜓 = 0
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2 ℎ2
After putting the value of potential energy of the electron-nucleus system in equation (250), we get
𝜕 2 𝜓 𝜕 2 𝜓 𝜕 2 𝜓 8𝜋 2 𝑚 𝑍𝑒 2 (251)
+ + + (𝐸 + )𝜓 = 0
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2 ℎ2 𝑟
The above-mentioned second order differential equation is the Schrodinger wave equation for an electron
around the nucleus. However, since it is neither completely in cartesian nor completely in polar coordinates
(contains x, y, z as well as r variable), the solution is very much difficult. Therefore, recall the transformation
of cartesian coordinates to polar coordinates in three dimensions as given below.
Figure 13. Correlation between cartesian and polar coordinates in three dimensions.
In tringle AOP, the side OA is simply the z-coordinate and can be obtained as
𝑂𝐴 (252)
= 𝐶𝑜𝑠 𝜃 ⇒ 𝑂𝐴 = 𝑂𝑃 𝐶𝑜𝑠 𝜃 ⇒ 𝑧 = 𝑟 𝐶𝑜𝑠 𝜃
𝑂𝑃
Similarly, in AOP
𝐴𝑃 (253)
= 𝑆𝑖𝑛 𝜃 ⇒ 𝐴𝑃 = 𝑂𝑃 𝑆𝑖𝑛 𝜃 ⇒ 𝑂𝑄 = 𝑟 𝑆𝑖𝑛 𝜃
𝑂𝑃
no watermark.
In tringle BOQ, the side OB is simply the x-coordinate and can be obtained as
𝑂𝐵 (254)
= 𝐶𝑜𝑠 𝜙 ⇒ 𝑂𝐵 = 𝑂𝑄 𝐶𝑜𝑠 𝜙 ⇒ 𝑥 = 𝑟 𝑆𝑖𝑛 𝜃 𝐶𝑜𝑠 𝜙
𝑂𝑄
Since the side BQ equal to OC, BQ also represents the y-coordinate and can be obtained as
𝐵𝑄 (255)
= 𝑆𝑖𝑛 𝜙 ⇒ 𝐵𝑄 = 𝑂𝑄 𝑆𝑖𝑛 𝜙 ⇒ 𝑦 = 𝑟 𝑆𝑖𝑛 𝜃 𝑆𝑖𝑛 𝜙
𝑂𝑄
Now using equation (252-254), the equation (251) can be transformed to polar coordinates as given below.
1 𝜕 2 𝜕𝜓 1 𝜕 𝜕𝜓 1 𝜕 2 𝜓 8𝜋 2 𝜇 𝑍𝑒 2 (256)
(𝑟 ) + (𝑆𝑖𝑛𝜃 ) + + (𝐸 + )𝜓 = 0
𝑟 2 𝜕𝑟 𝜕𝑟 𝑟 2 𝑆𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝑟 2 𝑆𝑖𝑛2 𝜃 𝜕𝜙 2 ℎ2 𝑟
or
1 𝜕 2 𝜕𝜓 1 𝜕 𝜕𝜓 1 𝜕2𝜓 8𝜋 2 𝜇 𝑍𝑒 2 (257)
[ (𝑟 ) + (𝑆𝑖𝑛𝜃 ) + ] + (𝐸 + )𝜓 = 0
𝑟 2 𝜕𝑟 𝜕𝑟 𝑆𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝑆𝑖𝑛2 𝜃 𝜕𝜙 2 ℎ2 𝑟
Which is the Schrodinger wave equation for hydrogen and hydrogen-like species in polar coordinates.
 Separation of Variables
The wave function representing quantum mechanical states, in this case, is actually a function of
three variable r, θ and ϕ. Now, we know that it is easier to solve three differential equations with one variable
in each rather a single differential equation with three variables. Therefore, in order to separate variables,
consider that the wave function ψ is the multiplication of three individual functions as
𝜓(𝑟, 𝜃, 𝜙) = 𝜓(𝑟) × 𝜓(𝜃) × 𝜓(𝜙) = 𝑅. 𝛩. 𝛷 (258)
After putting the value of equation (258) in equation (257) and then multiplying throughout by r2, we get
𝜕 2 𝜕𝑅 𝛷𝑅 𝜕 𝜕𝛩 𝑅𝛩 𝜕 2 𝛷 8𝜋 2 𝜇𝑟 2 𝑍𝑒 2 (259)
𝛩𝛷 (𝑟 )+ (𝑆𝑖𝑛𝜃 ) + + (𝐸 + ) 𝛩𝛷𝑅 = 0
𝜕𝑟 𝜕𝑟 𝑆𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝑆𝑖𝑛2 𝜃 𝜕𝜙 2 ℎ2 𝑟
Furthermore, divide equation (259) throughout 𝛩𝛷𝑅 i.e.
1 𝜕 2 𝜕𝑅 1 1 𝜕 𝜕𝛩 1 1 𝜕 2 𝛷 8𝜋 2 𝜇𝑟 2 𝑍𝑒 2 (260)
(𝑟 )+ (𝑆𝑖𝑛𝜃 ) + + (𝐸 + )=0
𝑅 𝜕𝑟 𝜕𝑟 𝛩 𝑆𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝛷 𝑆𝑖𝑛2 𝜃 𝜕𝜙 2 ℎ2 𝑟
or
1 𝜕 2 𝜕𝑅 8𝜋 2 𝜇𝑟 2 𝑍𝑒 2 1 1 𝜕 𝜕𝛩 1 1 𝜕2𝛷 (261)
(𝑟 )+ (𝐸 + ) = − (𝑆𝑖𝑛𝜃 ) −
𝑅 𝜕𝑟 𝜕𝑟 ℎ2 𝑟 𝛩 𝑆𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝛷 𝑆𝑖𝑛2 𝜃 𝜕𝜙 2
The above equation holds true if we put both sides equal to a constant β i.e.
no watermark.
1 𝜕 2 𝜕𝑅 8𝜋 2 𝜇𝑟 2 𝑍𝑒 2 (262)
(𝑟 )+ (𝐸 + )=𝛽
𝑅 𝜕𝑟 𝜕𝑟 ℎ2 𝑟
and
1 1 𝜕 𝜕𝛩 1 1 𝜕2𝛷 (263)
(𝑆𝑖𝑛𝜃 ) + = −𝛽
𝛩 𝑆𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝛷 𝑆𝑖𝑛2 𝜃 𝜕𝜙 2
The equation (262) contains only r variable, and therefore, is called as the “radial equation”. However, the
equation (263) still contains two variable, and thus, needs further separation. To do so, first multiply equation
(263) throughout by 𝑆𝑖𝑛2 𝜃 i.e.
𝑆𝑖𝑛𝜃 𝜕 𝜕𝛩 1 𝜕2𝛷 (264)

(𝑆𝑖𝑛𝜃 ) + = −𝛽 𝑆𝑖𝑛2 𝜃
𝛩 𝜕𝜃 𝜕𝜃 𝛷 𝜕𝜙 2
or
𝑆𝑖𝑛𝜃 𝜕 𝜕𝛩 1 𝜕2𝛷 (265)

(𝑆𝑖𝑛𝜃 ) + 𝛽 𝑆𝑖𝑛2 𝜃 = −
𝛩 𝜕𝜃 𝜕𝜃 𝛷 𝜕𝜙 2
The above equation also holds true if we put both sides equal to a constant m2 i.e.
𝑆𝑖𝑛𝜃 𝜕 𝜕𝛩 (266)
(𝑆𝑖𝑛𝜃 ) + 𝛽 𝑆𝑖𝑛2 𝜃 = 𝑚2
𝛩 𝜕𝜃 𝜕𝜃
and
1 𝜕2𝛷 (267)
= −𝑚2
𝛷 𝜕𝜙 2
The equation (266) contains only θ variable, and therefore, is called as “theta equation”. Likewise, the equation
(267) contains only ϕ variable, and therefore, is called as “phi equation”.
 Solutions of R(r), Θ(θ) and Φ(ϕ) Equations
The single variable equations obtained after separation of variables can be solved separately to yield
r, θ and ϕ-dependent functions which then are multiplied give total wave function.
1. The solution of Φ(ϕ) equation: Recall and rearrange the differential equation obtained after separation of
variables having ϕ dependence i.e.
1 𝜕2𝛷 𝜕𝛷 (268)
= −𝑚2 ⇒ + 𝑚2 𝛷 = 0
𝛷 𝜕𝜙 2 𝜕𝜙
The general solution of such an equation is
𝛷(𝜙) = 𝑁𝑒 𝑖𝑚𝜙 (269)
no watermark.
Where N represents the normalization constant. The wavefunction given above will be acceptable only if m
has integer value i.e. 0, ±1, ±2, etc. This can be understood in terms of single-valued, continuous and finite
nature of quantum states.
i) The boundary condition for function Φ: If we replace the angle “ϕ” with “ϕ + 2π”, the position of point under
consideration should remain the same i.e.
𝛷(𝜙 + 2𝜋) = 𝛷(𝜙) (270)
Therefore
𝑁𝑒 𝑖𝑚(𝜙+2𝜋) = 𝑁𝑒 𝑖𝑚𝜙 (271)
𝑒 𝑖𝑚(𝜙+2𝜋) = 𝑒 𝑖𝑚𝜙 (272)
𝑒 𝑖𝑚𝜙 . 𝑒 𝑖𝑚2𝜋 = 𝑒 𝑖𝑚𝜙 (273)
𝑒 𝑖𝑚2𝜋 = 𝑒 𝑖𝑚𝜙 𝑒 −𝑖𝑚𝜙 (274)
𝑒 𝑖𝑚2𝜋 = 𝑒 𝑖𝑚𝜙−𝑖𝑚𝜙 = 𝑒 0 (275)
𝑒 𝑖𝑚2𝜋 = 1 (276)
Since we know from the Euler’s expansion 𝑒 𝑖𝑥 = 𝐶𝑜𝑠 𝑥 + 𝑖 𝑆𝑖𝑛 𝑥, the equation (276) takes the form
𝑒 𝑖𝑚2𝜋 = 𝐶𝑜𝑠 2𝜋𝑚 + 𝑖 𝑆𝑖𝑛 2𝜋𝑚 (277)
𝐶𝑜𝑠 2𝜋𝑚 + 𝑖 𝑆𝑖𝑛 2𝜋𝑚 = 1 (278)
The relation holds true only when we use 𝑚 = 0, ±1, ±2, ±3, ±4, etc.
ii) The normalization constant for function Φ: In order to determine the normalization constant for the Φ
2𝜋 (279)
∫ 𝛷∗ 𝛷 𝑑𝜙 = 1
0
2𝜋 (280)
𝑁 ∫ 𝑒 𝑖𝑚𝜙 . 𝑒 −𝑖𝑚𝜙 𝑑𝜙 = 1
2
2𝜋 2𝜋 (281)
2 𝑖𝑚𝜙−𝑖𝑚𝜙 2 0
𝑁 ∫ 𝑒 𝑑𝜙 = 𝑁 ∫ 𝑒 𝑑𝜙 = 1
0 0
no watermark.
𝑁 2 [𝜙]2𝜋 2
0 = 𝑁 [2𝜋] = 1 (282)
or
(283)
1
𝑁=√
2𝜋
After using the value of normalization constant in equation (269), we get
(284)
1
𝛷𝑚 (𝜙) = √ 𝑒 𝑖𝑚𝜙
2𝜋
Which is the complete solution of ϕ-equation.
Table 1. Complex and real forms of some normalized Φ-functions.
|𝑚| Complex form Real form
0
1 1
𝛷0 (𝜙) = √ 𝛷0 (𝜙) = √
2𝜋 2𝜋
1
1 1
𝛷+1 (𝜙) = √ 𝑒 𝑖𝜙 𝛷+1 (𝜙) = √ 𝐶𝑜𝑠 𝜙
2𝜋 𝜋
1 1
𝛷−1 (𝜙) = √ 𝑒 −𝑖𝜙 𝛷−1 (𝜙) = √ 𝑆𝑖𝑛 𝜙
2𝜋 𝜋
2
1 1
𝛷+2 (𝜙) = √ 𝑒 𝑖2𝜙 𝛷+2 (𝜙) = √ 𝐶𝑜𝑠 (2𝜙)
2𝜋 𝜋
1 −𝑖2𝜙 1
𝛷−2 (𝜙) = √ 𝑒 𝛷−2 (𝜙) = √ 𝑆𝑖𝑛 (2𝜙)
2𝜋 𝜋
3
1 1
𝛷+3 (𝜙) = √ 𝑒 𝑖3𝜙 𝛷+3 (𝜙) = √ 𝐶𝑜𝑠 (3𝜙)
2𝜋 𝜋
1 −𝑖3𝜙 1
𝛷−3 (𝜙) = √ 𝑒 𝛷−3 (𝜙) = √ 𝑆𝑖𝑛 (3𝜙)
2𝜋 𝜋
no watermark.
2. The solution of Θ(θ) equation: Recall and rearrange the differential equation obtained after separation of
variables having θ-dependence i.e.
𝑆𝑖𝑛𝜃 𝜕 𝜕𝛩 (285)
(𝑆𝑖𝑛𝜃 ) + 𝛽 𝑆𝑖𝑛2 𝜃 = 𝑚2
𝛩 𝜕𝜃 𝜕𝜃
or
𝜕 𝜕𝛩 (286)
𝑆𝑖𝑛 𝜃 (𝑆𝑖𝑛 𝜃 ) + 𝛩𝛽𝑆𝑖𝑛2 𝜃 − 𝑚2 𝛩 = 0
𝜕𝜃 𝜕𝜃
Now dividing the above equation by 𝑆𝑖𝑛2 𝜃, we get
1 𝜕 𝜕𝛩 𝑚2 𝛩 (287)
(𝑆𝑖𝑛 𝜃 ) + 𝛩𝛽 − =0
or
1 𝜕 𝜕𝛩 𝑚2 (288)
(𝑆𝑖𝑛 𝜃 ) + (𝛽 − )𝛩 = 0
After defining a new variable 𝑥 = 𝐶𝑜𝑠 𝜃, we have
𝑆𝑖𝑛2 𝜃 + 𝐶𝑜𝑠 2 𝜃 = 1 (289)
𝑆𝑖𝑛2 𝜃 = 1 − 𝐶𝑜𝑠 2 𝜃 (290)
𝑆𝑖𝑛 𝜃 = √1 − 𝐶𝑜𝑠 2 𝜃 (291)
𝑆𝑖𝑛 𝜃 = √1 − 𝑥 2 (292)
Also, since we assumed 𝑥 = 𝐶𝑜𝑠 𝜃, the first derivative w.r.t. θ will be
𝜕𝑥 (293)
𝜕𝜃
The derivative of Θ function w.r.t. θ can be rewritten as
𝜕𝛩 𝜕𝛩 𝜕𝑥 (294)
= .
𝜕𝜃 𝜕𝑥 𝜕𝜃
After putting the values of 𝜕𝑥/𝜕𝜃 from equation (293) in equation (294), we get
𝜕𝛩 𝜕𝛩 (295)
𝜕𝜃 𝜕𝑥
After removing Θ from both sides
no watermark.
𝜕 𝜕 (296)
𝜕𝜃 𝜕𝑥
Multiplying both sides of equation (295) by 𝑆𝑖𝑛 𝜃, we have
𝜕𝛩 𝜕𝛩 (297)
𝑆𝑖𝑛 𝜃 = −𝑆𝑖𝑛2 𝜃
𝜕𝜃 𝜕𝑥
𝜕𝛩 𝜕𝛩 (298)
𝑆𝑖𝑛 𝜃 = −(1 − 𝑥 2 )
𝜕𝜃 𝜕𝑥
Now, after putting the values of equation (296) and (298) in equation (288), we get
1 𝜕 𝜕𝛩 𝑚2 (299)
(−𝑆𝑖𝑛 𝜃 ) [−(1 − 𝑥 2 ) ] + (𝛽 − )𝛩 = 0
𝑆𝑖𝑛 𝜃 𝜕𝑥 𝜕𝑥 1 − 𝑥2
𝜕 𝜕𝛩 𝑚2 (300)
[(1 − 𝑥 2 ) ] + (𝛽 − )𝛩 = 0
𝜕𝑥 𝜕𝑥 1 − 𝑥2
The equation given above is a Legendre’s polynomial and has physical significance only in the range of 𝑥 =
+1 to − 1. Therefore, consider that one more form of Θ function so that this condition is satisfied i.e.
𝑚
𝛩(𝜃) = (1 − 𝑥 2 ) 2 . 𝑋(𝑥) (301)
Where X is a function depending upon variable x. The differentiation of the above equation w.r.t. x yields
𝜕𝛩 𝑚 𝑚 𝑑𝑋 (302)
= −𝑚𝑥(1 − 𝑥 2 ) 2 −1 . 𝑋 + (1 − 𝑥 2 ) 2 .
𝜕𝑥 𝑑𝑥
After multiplying the above equation by 1 − 𝑥 2 and 𝜕/𝜕𝑥, we get
𝜕 𝜕𝛩 𝜕 𝑚 𝑚 𝑑𝑋 (303)
[(1 − 𝑥 2 ) ] = [−𝑚𝑥(1 − 𝑥 2 ) 2 . 𝑋 + (1 − 𝑥 2 ) 2 +1 . ]
𝜕𝑥 𝜕𝑥 𝜕𝑥 𝑑𝑥
𝑚 𝑚
= [−𝑚(1 − 𝑥 2 )𝑚/2 + 𝑚2 𝑥 2 (1 − 𝑥 2 ) 2 −1 ] 𝑋 − [2𝑥(𝑚 + 1)(1 − 𝑥 2 ) 2 ] 𝑋 ′ (304)
𝑚
+ [(1 − 𝑥 2 ) 2 +1 ] 𝑋 ′′
Where 𝜕/𝜕𝑥 and 𝜕 2 /𝜕𝑥 2 are represented by the symbol 𝑋 ′ and 𝑋 ” , respectively. Now, after using the value of
equation (301) and equation (304) in equation (300), we get
𝑚 𝑚
[−𝑚(1 − 𝑥 2 )𝑚/2 + 𝑚2 𝑥 2 (1 − 𝑥 2 ) 2 −1 ] 𝑋 − [2𝑥(𝑚 + 1)(1 − 𝑥 2 ) 2 ] 𝑋 ′ (305)
𝑚 𝑚2 𝑚
+ [(1 − 𝑥 2 ) 2 +1 ] 𝑋 ′′ + (𝛽 − ) (1 − 𝑥 2) 2
.𝑋 = 0
1 − 𝑥2
Dividing the above expression by (1 − 𝑥 2 )𝑚/2 , we have
no watermark.
(1 − 𝑥 2 )𝑋 ′′ − 2(𝑚 + 1)𝑥𝑋 ′ + [𝛽 − 𝑚(𝑚 + 1)]𝑋 = 0 (306)
or
(1 − 𝑥 2 )𝑋 ′′ − 2𝛼𝑥𝑋 ′ + 𝜆𝑋 = 0 (307)
Where 𝛼 = 𝑚 + 1 and 𝜆 = 𝛽 − 𝑚(𝑚 + 1). Now assume that the function X can be expressed as a power
series expansion as given below.
𝑋 = 𝑎0 + 𝑎1 𝑥 + 𝑎2 𝑥 2 + 𝑎3 𝑥 3 … … … … (308)
𝑋 ′ = 𝑎1 + 2𝑎2 𝑥 + 3𝑎3 𝑥 2 … … … … (309)
𝑋 ′′ = 2𝑎2 + 6𝑎3 𝑥 + 12𝑎4 𝑥 2 … … … … (310)
Putting values of equation (308-310) in equation (307), we get
(1 − 𝑥 2 )(2𝑎2 + 6𝑎3 𝑥 + 12𝑎4 𝑥 2 + 20𝑎5 𝑥 3 ) − 2𝛼𝑥(𝑎1 + 2𝑎2 𝑥 + 3𝑎3 𝑥 2 + 4𝑎4 𝑥 3 ) (311)

+ 𝜆(𝑎0 + 𝑎1 𝑥 + 𝑎2 𝑥 2 + 𝑎3 𝑥 3 ) = 0
or
(2𝑎2 + 𝜆𝑎0 ) + [6𝑎3 + (𝜆 − 2𝛼)𝑎1 ]𝑥 + [12𝑎4 + (𝜆 − 2𝛼 − 2)𝑎2 ]𝑥 2 … … … = 0 (312)
The above equation is satisfied only if each term on the left-hand side is individually equal to zero i.e.
coefficients of each power of x are vanish. The general expression for the coefficients must follow the condition
given below.+
(𝑛 + 1)(𝑛 + 2)𝑎𝑛+2 + [𝜆 − 2𝑛𝛼 − 𝑛(𝑛 − 1)]𝑎𝑛 = 0 (313)
Where 𝑛 = 0, 1, 2, 3 etc. Summarizing the result, we can write
2𝑛𝛼 + 𝑛(𝑛 − 1) − 𝜆 (314)

𝑎𝑛+2 = 𝑎𝑛
(𝑛 + 1)(𝑛 + 2)
After putting values of α and λ in equation (314), we get
𝑎𝑛+2 (𝑛 + 𝑚)(𝑛 + 𝑚 + 1) − 𝛽 (315)

=
𝑎𝑛 (𝑛 + 1)(𝑛 + 2)
Which is the Recursion formula for the coefficients of the power of x. Now, in order to obtain a valid
wavefunction, the power series must contain a finite number of terms which is possible only if numerator
becomes zero i.e.
(𝑛 + 𝑚)(𝑛 + 𝑚 + 1) − 𝛽 = 0 (316)
𝛽 = (𝑛 + 𝑚)(𝑛 + 𝑚 + 1) (317)
no watermark.
Since we know that m as well n both are the whole numbers, their sum must also be a whole number. Therefore,
the sum of n and m can be replaced by another whole number symbolized by l i.e.
𝛽 = 𝑙(𝑙 + 1) (318)
Where 𝑙 = 0, 1, 2, 3 etc. After putting the value of β from equation (318) in equation (300), we get
𝜕 2
𝜕𝛩 𝑚2 (319)
[(1 − 𝑥 ) ] + [𝑙(𝑙 + 1) − ]𝛩 = 0
𝜕𝑥 𝜕𝑥 1 − 𝑥2
The general solution of equation (319) is
𝛩 = 𝑁𝑃𝑙𝑚 (𝑥) = 𝑁𝑃𝑙𝑚 (𝐶𝑜𝑠 𝜃) (320)
Where N is the normalization constant and 𝑃𝑙𝑚 (𝑥) is the associated “Legendre function” which is defined as
given below.
𝑑𝑚 𝑃𝑙 (𝑥) (321)
𝑃𝑙𝑚 (𝑥) = (1 − 𝑥 2 )𝑚/2
𝑑𝑥 𝑚
Where 𝑃𝑙 (𝑥) is the Legendre polynomial given by
1 𝑑𝑙 (𝑥 2 − 1)𝑙 (322)
𝑃𝑙 (𝑥) =
2𝑙 𝑙! 𝑑𝑥 𝑙
In order to proceed further, we must discuss the concept of orthogonality and the normalization of the
“Legendre’s function”.
i) Orthogonality of associated Legendre’s function: The orthogonality of the associated Legendre’s polynomial
follows the conditions given below.
+1 (323)
∫ 𝑃𝑘𝑚 (𝑥) 𝑃𝑙𝑚 (𝑥) =0 𝑖𝑓 𝑘 ≠ 𝑙
−1
+1 (324)
2 (𝑙 + 𝑚)!
∫ 𝑃𝑘𝑚 (𝑥) 𝑃𝑙𝑚 (𝑥) = 𝑖𝑓 𝑘 = 𝑙
(2𝑙 + 1) (𝑙 − 𝑚)!
−1
ii) Normalization of associated Legendre’s function: The normalization of the associated Legendre’s
polynomial follows the conditions given below.
+1 (325)
∗
∫ 𝛩𝑚,𝑙 𝛩𝑚,𝑙 (𝑑𝜃) = 1
−1
no watermark.
+1 (326)
2
𝑁 ∫ 𝑃𝑘𝑚 (𝑥) 𝑃𝑙𝑚 (𝑥) 𝑑𝑥 =1
−1
2 (𝑙 + 𝑚)! (327)
𝑁2. =1
(2𝑙 + 1) (𝑙 − 𝑚)!
(328)
(2𝑙 + 1)(𝑙 − 𝑚)!
𝑁=√
2(𝑙 + 𝑚)!
Using the value of normalization constant in equation (320), we get
(329)
(2𝑙 + 1)(𝑙 − 𝑚)! 𝑚
𝛩𝑙,𝑚 (𝜃) = √ . 𝑃𝑙 (𝐶𝑜𝑠 𝜃)
2(𝑙 + 𝑚)!
Which is the complete solution of Θ-equation.
Table 2. Some normalized Θ-functions and corresponding spherical harmonics.
Θ-functions Spherical harmonics
1
𝛩0,0 = 1 1
√2 𝛶0,0 = .√
√2 2𝜋
3 3 1
𝛩1,0 = √ 𝐶𝑜𝑠 𝜃 𝛶1,0 = √ 𝐶𝑜𝑠 𝜃.
2 2 √2𝜋
3 3 1
𝛩1,±1 = √ 𝑆𝑖𝑛 𝜃 𝛶1,±1 = √ 𝑆𝑖𝑛 𝜃. √ 𝑒 ±𝑖𝜙
4 4 2𝜋
5 5 1
𝛩2,0 = √ (3𝐶𝑜𝑠 2 𝜃 − 1) 𝛶2,0 = √ (3𝐶𝑜𝑠 2 𝜃 − 1).
8 8 √2𝜋
15 15 1
𝛩2,±1 = √ 𝑆𝑖𝑛 𝜃 𝐶𝑜𝑠 𝜃 𝛶2,±1 = √ 𝑆𝑖𝑛 𝜃 𝐶𝑜𝑠 𝜃. √ 𝑒 ±𝑖𝜙
4 4 2𝜋
15 15 1
𝛩2,±2 = √ 𝑆𝑖𝑛2 𝜃 𝛶2,±2 = √ 𝑆𝑖𝑛2 𝜃. √ 𝑒 ±𝑖2𝜙
16 16 2𝜋
no watermark.
3. The solution of R(r) equation: Recall and rearrange the differential equation obtained after separation of
variables having r-dependence i.e.
1 𝜕 2 𝜕𝑅 8𝜋 2 𝜇𝑟 2 𝑍𝑒 2 (330)
(𝑟 )+ (𝐸 + )=𝛽
𝑅 𝜕𝑟 𝜕𝑟 ℎ2 𝑟
After putting ħ = h/2π and rearranging, we get
1 𝜕 2 𝜕𝑅 2𝜇𝑟 2 (331)
(𝑟 ) + 2 (𝐸 − 𝑉) = 𝛽
𝑅 𝜕𝑟 𝜕𝑟 ħ
After multiplying by R on both sides and then dividing by r2 throughout, we get
1 𝜕 2 𝜕𝑅 2𝜇 𝛽𝑅 (332)
2
(𝑟 ) + 2 (𝐸 − 𝑉)𝑅 = 2
𝑟 𝜕𝑟 𝜕𝑟 ħ 𝑟
Now, as we know from the solution of Θ-equation that 𝛽 = 𝑙(𝑙 + 1), the above equation takes the form
1 𝜕 2 𝜕𝑅 2𝜇 𝑙(𝑙 + 1)𝑅 (333)

2
(𝑟 ) + 2 (𝐸 − 𝑉)𝑅 =
𝑟 𝜕𝑟 𝜕𝑟 ħ 𝑟2
1 𝜕 2 𝜕𝑅 2𝜇 𝑙(𝑙 + 1)𝑅 (334)
2
(𝑟 ) + 2 (𝐸 − 𝑉)𝑅 − =0
or
1 2 𝜕2𝑅 𝜕𝑅 2𝜇 𝑙(𝑙 + 1) (335)

2
[𝑟 2
+ 2𝑟 ] + [ 2 (𝐸 − 𝑉) − ]𝑅 = 0
𝜕 2 𝑅 2 𝜕𝑅 2𝜇 𝑙(𝑙 + 1) (336)
[ 2+ ] + [ 2 (𝐸 − 𝑉) − ]𝑅 = 0
𝜕𝑟 𝑟 𝜕𝑟 ħ 𝑟2
Putting the value of potential energy for atomic hydrogen or hydrogen-like species again in the above equation,
we get
𝜕 2 𝑅 2 𝜕𝑅 2𝜇𝐸 2𝜇𝑍𝑒 2 𝑙(𝑙 + 1) (337)

+ + [ + 2 − ]𝑅 = 0
𝜕𝑟 2 𝑟 𝜕𝑟 ħ2 ħ 𝑟 𝑟2
As we know from the classical mechanics that elliptical orbits represent bound states have energies less than
zero whereas hyperbolic orbits represent unbound states have energies greater than zero. Now assume that
electron around the nucleus is bound somehow i.e.
2𝜇𝐸 𝜇𝑍𝑒 2 (338)

− = 𝛼2 𝑎𝑛𝑑 =𝜆
ħ2 ħ2 𝛼
Using equation (338) in equation (337), we get
no watermark.
𝜕 2 𝑅 2 𝜕𝑅 2
2𝛼𝜆 𝑙(𝑙 + 1) (339)
+ + [−𝛼 + − ]𝑅 = 0
𝜕𝑟 2 𝑟 𝜕𝑟 𝑟 𝑟2
At this stage, we need to define a new variable 𝜌 = 2𝛼𝑟, so that
𝜕𝜌 (340)
= 2𝛼
𝜕𝑟
Which follows
𝜕𝑅 𝜕𝑅 𝜕𝜌 𝜕𝑅 (341)
= . = 2𝛼
𝜕𝑟 𝜕𝜌 𝜕𝑟 𝜕𝜌
Also
𝜕2𝑅 𝜕 𝜕𝑅 𝜕 𝜕𝑅 𝜕 𝜕𝜌 𝜕𝑅 𝜕𝜌 𝜕 𝜕𝑅 (341)
= [ ] = [2𝛼 ] = [2𝛼 ] = [2𝛼 ]
𝜕𝑟 2 𝜕𝑟 𝜕𝑟 𝜕𝑟 𝜕𝜌 𝜕𝑟 𝜕𝜌 𝜕𝜌 𝜕𝑟 𝜕𝜌 𝜕𝜌
𝜕2𝑅 𝜕 𝜕𝑅 2
𝜕2𝑅 (342)
= 2𝛼 [2𝛼 ] = 4𝛼
𝜕𝑟 2 𝜕𝜌 𝜕𝜌 𝜕𝜌2
After using the values of 𝜕𝑅/𝜕𝑟 and 𝜕 2 𝑅/𝜕𝑟 2 from equation (341) and equation (342) in equation (339), we
get the following.
𝜕2𝑅 2
2
𝜕𝑅 2
2𝛼𝜆 𝑙(𝑙 + 1) (343)
4𝛼 + 2𝛼 + [−𝛼 + − ]𝑅 = 0
𝜕𝜌2 𝑟 𝜕𝜌 𝑟 𝑟2
Now divide the above equation by 4𝛼 2 i.e.
𝜕 2 𝑅 1 𝜕𝑅 1 𝜆 𝑙(𝑙 + 1) (344)
2
+ + [− + − ]𝑅 = 0
𝜕𝜌 𝛼𝑟 𝜕𝜌 4 2𝛼𝑟 4𝛼 2 𝑟 2
Using 𝜌 = 2𝛼𝑟, we get
𝜕 2 𝑅 2 𝜕𝑅 1 𝜆 𝑙(𝑙 + 1) (345)
2
+ + [− + − ]𝑅 = 0
𝜕𝜌 𝜌 𝜕𝜌 4 𝜌 𝜌2
When 𝜌 → ∞, the above equation takes the form
𝜕2𝑅 1 (346)
− 𝑅=0
𝜕𝜌2 4
The general solutions of the differential equation given above are
𝑅(𝜌) = 𝑒 +𝜌/2 𝑎𝑛𝑑 𝑅(𝜌) = 𝑒 −𝜌/2 (347)
The function 𝑅(𝜌) = 𝑒 +𝜌/2 becomes ∞ when ρ = ∞, and hence, is not acceptable. Therefore, we are left with
no watermark.
𝑅(𝜌) = 𝑒 −𝜌/2 (348)
Since the acceptable solution given above is valid only at very large values of ρ, it is quite reasonable to think
that the exact solution may also contain some pre-exponential part to attain validity at all values of ρ. Therefore,
after incorporating some ρ-dependent unknown function ‘F(ρ)’ in equation (348), we get
𝑅(𝜌) = 𝐹(𝜌) 𝑒 −𝜌/2 (349)
Differentiating above equation with w.r.t ρ at first and second order and then putting the values of 𝑅(𝜌),
𝜕𝑅/𝜕𝜌 and 𝜕 2 𝑅/𝜕𝜌2 in equation (345), we get
𝜕2𝐹 2 𝜕𝐹 1 𝜆 𝑙(𝑙 + 1) (350)

2
+ ( − 1) + [− + − ]𝐹 = 0
𝜕𝜌 𝜌 𝜕𝜌 𝜌 𝜌 𝜌2
For simplification, put 𝜕 2 𝑅/𝜕𝜌2 = 𝐹 ′′ and 𝜕𝑅/𝜕𝜌 = 𝐹 ′ i.e.
2 1 𝜆 𝑙(𝑙 + 1) (351)
𝐹 ′′ + ( − 1) 𝐹 ′ + [− + − ]𝐹 = 0
𝜌 𝜌 𝜌 𝜌2
Hence, the problem has been reduced to the determination of the solution of F which can be assumed as
𝐹(𝜌) = 𝜌 𝑠 𝐺(𝜌) (352)
Where 𝐺(𝜌) represents a power series expansion of ρ i.e.
𝐺(𝜌) = 𝑎0 + 𝑎1 𝜌 + 𝑎2 𝜌2 + 𝑎3 𝜌3 … (353)
Or we can say that

𝑘=∞ (354)
𝑘
𝐺(𝜌) = ∑ 𝑎𝑘 𝜌
𝑘=0
It is also worthy to mention that 𝑎0 ≠ 0. Now differentiating equation (352) w.r.t. ρ, we get
𝐹 ′ (𝜌) = 𝑠𝜌 𝑠−1 𝐺 + 𝜌 𝑠 𝐺 ′ (355)
The double derivative of the same will be
𝐹 ′′ (𝜌) = 𝑠(𝑠 − 1)𝜌 𝑠−2 𝐺 + 2𝑠𝜌 𝑠−1 𝐺 ′ + 𝜌 𝑠 𝐺 ′′ (356)
After putting the values of 𝐹(𝜌), 𝐹 ′ (𝜌) and 𝐹 ′′ (𝜌) from equation (352, 355, 356) into equation (351), we get
2 (357)
𝑠(𝑠 − 1)𝜌 𝑠−2 𝐺 + 2𝑠𝜌 𝑠−1 𝐺 ′ + 𝜌 𝑠 𝐺 ′′ + ( − 1) [𝑠𝜌 𝑠−1 𝐺 + 𝜌 𝑠 𝐺 ′ ]
𝜌
1 𝜆 𝑙(𝑙 + 1) 𝑠
+ [− + − ]𝜌 𝐺 = 0
𝜌 𝜌 𝜌2
no watermark.
Multiplying throughout by 4𝜌2 , we get
4𝜌2 𝑠(𝑠 − 1)𝜌 𝑠−2 𝐺 + 4𝜌2 . 2𝑠𝜌 𝑠−1 𝐺 ′ + 4𝜌2 . 𝜌 𝑠 𝐺 ′′ + (8𝜌 − 4𝜌2 )[𝑠𝜌 𝑠−1 𝐺 + 𝜌 𝑠 𝐺 ′ ] (358)
+ [−4𝜌 + 4𝜌𝜆 − 4𝑙(𝑙 + 1)]𝜌 𝑠 𝐺 = 0
or
4𝑠(𝑠 − 1)𝜌 𝑠 𝐺 + 8𝑠𝜌 𝑠+1 𝐺 ′ + 4𝜌 𝑠+2 𝐺 ′′ + 8𝑠𝜌 𝑠 𝐺 − 4𝑠𝜌 𝑠+1 𝐺 + 8𝜌 𝑠+1 𝐺 ′ (359)
− 4𝜌 𝑠+2 𝐺 ′ − 4𝜌 𝑠+1 𝐺 + 4𝜆𝜌 𝑠+1 𝐺 − 4𝑙(𝑙 + 1)𝜌 𝑠 𝐺 = 0
or
4𝑠(𝑠 − 1)𝜌 𝑠 𝐺 + 8𝑠𝜌 𝑠 𝐺 − 4𝑠𝜌 𝑠+1 𝐺 − 4𝜌 𝑠+1 𝐺 + 4𝜆𝜌 𝑠+1 𝐺 − 4𝑙(𝑙 + 1)𝜌 𝑠 𝐺 (360)
+ 8𝑠𝜌 𝑠+1 𝐺 ′ + 8𝜌 𝑠+1 𝐺 ′ − 4𝜌 𝑠+2 𝐺 ′ + 4𝜌 𝑠+2 𝐺 ′′ = 0
or
[4𝑠(𝑠 − 1)𝜌 𝑠 + 8𝑠𝜌 𝑠 − 4𝑠𝜌 𝑠+1 − 4𝜌 𝑠+1 + 4𝜆𝜌 𝑠+1 − 4𝑙(𝑙 + 1)𝜌 𝑠 ]𝐺 (361)
+ [8𝑠𝜌 𝑠+1 + 8𝜌 𝑠+1 − 4𝜌 𝑠+2 ]𝐺 ′ + 4𝜌 𝑠+2 𝐺 ′′ = 0
Dividing throughout by 𝜌 𝑠 , we get
[4𝑠(𝑠 − 1) + 8𝑠 − 4𝑠𝜌 − 4𝜌 + 4𝜆𝜌 − 4𝑙(𝑙 + 1)]𝐺 + [8𝑠𝜌 + 8𝜌 − 4𝜌2 ]𝐺 ′ (362)

2 ′′
+ 4𝜌 𝐺 = 0
If 𝜌 = 0, the function 𝐺(𝜌) = 𝑎0 and the above equation takes the form
[4𝑠(𝑠 − 1) + 8𝑠 − 4𝑙(𝑙 + 1)]𝑎0 = 0 (363)
Since 𝑎0 ≠ 0, the quantity that must be equal to zero to satisfy the above result is
4𝑠(𝑠 − 1) + 8𝑠 − 4𝑙(𝑙 + 1) = 0 (364)
𝑠(𝑠 − 1) + 2𝑠 − 𝑙(𝑙 + 1) = 0 (365)
𝑠(𝑠 + 1) − 𝑙(𝑙 + 1) = 0 (366)
𝑠(𝑠 + 1) = 𝑙(𝑙 + 1)
Which implies that
𝑠=𝑙 𝑜𝑟 𝑠 = −(𝑙 + 1) (367)
Now, if we put 𝑠 = −(𝑙 + 1) the first term in the function F(ρ) becomes 𝑎0 /0𝑙+1 at 𝜌 = 0 which infinite, and
hence is not an acceptable solution. Thus, the only we are left with is 𝑠 = 𝑙; after using the same in equation
(362), we get
no watermark.
[4𝑙(𝑙 − 1) + 8𝑙 − 4𝑙𝜌 − 4𝜌 + 4𝜆𝜌 − 4𝑙(𝑙 + 1)]𝐺 + [8𝑙𝜌 + 8𝜌 − 4𝜌2 ]𝐺 ′ + 4𝜌2 𝐺 ′′ (368)

=0
[−4𝑙𝜌 − 4𝜌 + 4𝜆𝜌]𝐺 + [8𝑙𝜌 + 8𝜌 − 4𝜌2 ]𝐺 ′ + 4𝜌2 𝐺 ′′ = 0 (369)
Dividing the above equation by 4𝜌, we get
[−𝑙 − 1 + 𝜆]𝐺 + [2𝑙 + 2 − 𝜌]𝐺 ′ + 𝜌𝐺 ′′ = 0 (370)
Now differentiating equation (353) at first and second order, we get

𝑘=∞ (371)
′ (𝜌) 1−1 2−1 3−1
𝐺 = 𝑎1 1𝜌 + 𝑎2 2𝜌 + 𝑎3 3𝜌 … = ∑ 𝑎𝑘 . 𝑘. 𝜌𝑘−1
𝑘=0
Similarly
𝑘=∞ (372)
′′ (𝜌) 2−2 3−2
𝐺 = 𝑎2 . 2. (2 − 1)𝜌 + 𝑎3 . 3. (3 − 1)𝜌 … = ∑ 𝑎𝑘 . 𝑘. (𝑘 − 1). 𝜌𝑘−2
𝑘=0
After using the values equation (354, 371, 372) into equation (370), we get
𝑘=∞ 𝑘=∞ 𝑘=∞ (373)
𝑘 𝑘−1
[−𝑙 − 1 + 𝜆] ∑ 𝑎𝑘 𝜌 + [2𝑙 + 2 − 𝜌] ∑ 𝑎𝑘 . 𝑘. 𝜌 + 𝜌 ∑ 𝑎𝑘 . 𝑘. (𝑘 − 1). 𝜌𝑘−2
𝑘=0 𝑘=0 𝑘=0
=0
The above equation holds true only if the coefficients of individual powers of ρ become zero. So, simplifying
equation (373) for two summation terms (ak and ak+1), we have
[−𝑙 − 1 + 𝜆][𝑎𝑘 𝜌𝑘 + 𝑎𝑘+1 𝜌𝑘+1 ] + [2𝑙 + 2 − 𝜌][𝑎𝑘 . 𝑘. 𝜌𝑘−1 + 𝑎𝑘+1 . (𝑘 + 1). 𝜌𝑘 ] (374)
𝑘−2 𝑘−1 ]
+ 𝜌[𝑎𝑘 . 𝑘. (𝑘 − 1). 𝜌 + 𝑎𝑘+1 . (𝑘 + 1). 𝑘. 𝜌 =0
−𝑙𝑎𝑘 𝜌𝑘 − 𝑎𝑘 𝜌𝑘 + 𝜆𝑎𝑘 𝜌𝑘 − 𝑙𝑎𝑘+1 𝜌𝑘+1 − 𝑎𝑘+1 𝜌𝑘+1 + 𝜆𝑎𝑘+1 𝜌𝑘+1 + 2𝑙𝑎𝑘 . 𝑘. 𝜌𝑘−1 (375)
+ 2𝑎𝑘 . 𝑘. 𝜌𝑘−1 − 𝜌𝑎𝑘 . 𝑘. 𝜌𝑘−1 + 2𝑙𝑎𝑘+1 . (𝑘 + 1). 𝜌𝑘 + 2𝑎𝑘+1 . (𝑘
+ 1). 𝜌𝑘 − 𝜌𝑎𝑘+1 . (𝑘 + 1). 𝜌𝑘 + 𝜌. 𝑎𝑘 . 𝑘. (𝑘 − 1). 𝜌𝑘−2
+ 𝜌. 𝑎𝑘+1 . (𝑘 + 1). 𝑘. 𝜌𝑘−1 = 0
Now putting a coefficient of 𝜌𝑘 equal to zero, we get
−𝑙𝑎𝑘 𝜌𝑘 − 𝑎𝑘 𝜌𝑘 + 𝜆𝑎𝑘 𝜌𝑘 − 𝑎𝑘 . 𝑘. 𝜌𝑘 + 2𝑙𝑎𝑘+1 . (𝑘 + 1). 𝜌𝑘 + 2𝑎𝑘+1 . (𝑘 + 1). 𝜌𝑘 (376)

𝑘
+ 𝑎𝑘+1 . (𝑘 + 1). 𝑘. 𝜌 = 0
−𝑙𝑎𝑘 − 𝑎𝑘 + 𝜆𝑎𝑘 − 𝑎𝑘 𝑘 + 2𝑙𝑎𝑘+1 (𝑘 + 1) + 2𝑎𝑘+1 (𝑘 + 1) + 𝑎𝑘+1 (𝑘 + 1)𝑘 = 0 (377)
or
no watermark.
[−𝑙 − 1 + 𝜆 − 𝑘]𝑎𝑘 + [2𝑙(𝑘 + 1) + 2(𝑘 + 1) + (𝑘 + 1)𝑘]𝑎𝑘+1 = 0 (378)
[2𝑙(𝑘 + 1) + 2(𝑘 + 1) + (𝑘 + 1)𝑘]𝑎𝑘+1 = −[−𝑙 − 1 + 𝜆 − 𝑘]𝑎𝑘 (379)
or
𝑙+1−𝜆+𝑘 (380)
𝑎𝑘+1 = 𝑎
2𝑙(𝑘 + 1) + 2(𝑘 + 1) + (𝑘 + 1)𝑘 𝑘
or
𝑙+1−𝜆+𝑘 (381)
𝑎𝑘+1 = 𝑎
(𝑘 + 1)(2𝑙 + 𝑘 + 2) 𝑘
The equation (384) is the recursion formula where k is an integer. This expression allows one to determine the
coefficient 𝑎𝑘+1 in terms of 𝑎𝑘 which is arbitrary.
Now, since the series 𝐺(𝜌) consists of the infinite number of terms, the function 𝐹(𝜌) becomes
infinite at a very large value of k i.e. infinite. Consequently, the function 𝑅(𝜌) will also become infinite if the
number of terms is not limited to a finite value. Therefore, we must break off the series to a finite number of
terms which is possible only if the numerator becomes zero i.e.
𝑙+1−𝜆+𝑘 =0 (382)
Define a new quantum number “n” at this stage as
𝜆 =𝑙+1+𝑘 =𝑛 (383)
Since l and k are integers, n can be 1, 2, 3. 4 …. and so on. Moreover, as 𝑛 ≥ 𝑙 + 1, the largest value that l can
have is 𝑛 − 1. Hence, the value of l has a domain ranging from 0 to 𝑛 − 1. Putting 𝜆 = 𝑛 in equation (370)
[−𝑙 − 1 + 𝑛]𝐺 + [2𝑙 + 2 − 𝜌]𝐺 ′ + 𝜌𝐺 ′′ = 0 (384)
Defining 2𝑙 + 1 = 𝑝 and 𝑛 + 𝑙 = 𝑞, we get
[𝑞 − 𝑝]𝐺 + [𝑝 + 1 − 𝜌]𝐺 ′ + 𝜌𝐺 ′′ = 0 (385)
The solution of the equation given above is the “associated Laguerre polynomial” multiplied by a constant
factor i.e.
𝑝
𝐺(𝑝) = 𝐶𝐿𝑞 (𝜌) = 𝐶𝐿2𝑙+1
𝑛+𝑙 (𝜌) (385)
The constant C can be set as normalization constant and “associated Laguerre polynomial” is
𝑘=𝑛−𝑙−1
(−1)𝑘+1 [(𝑛 + 𝑙)!]2 𝜌𝑘 (385)
𝐿2𝑙+1
𝑛+𝑙 (𝜌) = ∑
(𝑛 − 𝑙 − 1 − 𝑘)! (2𝑙 + 1 + 𝑘)! 𝑘!
𝑘=0
no watermark.
After using the value of 𝐹(𝜌) from equation (352) in equation (349), we get radial wavefunction as
𝑅(𝜌) = 𝜌 𝑠 𝐺(𝜌) 𝑒 −𝜌/2 (386)
Since 𝑠 = 𝑙 and also using 𝐺(𝑝) from equation (385), the above equation takes the form
𝑅𝑛,𝑙 (𝜌) = 𝐶 𝑒 −𝜌/2 𝜌𝑙 𝐿2𝑙+1

𝑛+𝑙 (𝜌) (387)
Now, after using the value of 𝐿2𝑙+1

𝑛+𝑙 (𝜌) from equation (385) in equation (387), we get
𝑘=𝑛−𝑙−1
(−1)𝑘+1 [(𝑛 + 𝑙)!]2 𝜌𝑘 (388)
−𝜌/2 𝑙
𝑅𝑛,𝑙 (𝜌) = 𝐶 𝑒 𝜌 ∑
(𝑛 − 𝑙 − 1 − 𝑘)! (2𝑙 + 1 + 𝑘)! 𝑘!
𝑘=0
i) The normalization constant for function R(r): In order to determine the normalization constant for the R
∞
(389)
2 (𝑟). 2
∫ 𝑅𝑛,𝑙 𝑟 . 𝑑𝑟 = 1
0
The factor r2 is introduced to convert the length dr into a volume around the center of the nucleus. At this
point, recall the value of ρ again but in terms of equation (338, 383) i.e.
2𝜇𝑍𝑒 2 𝑟 2𝜇𝑍𝑒 2 𝑟 2𝑍𝑟 𝜇𝑒 2 (390)

𝜌 = 2𝛼𝑟 = = = .
ħ2 𝜆 ħ2 𝑛 𝑛 ħ2
Since 𝑎0 = ħ2 /𝜇𝑒 2 i.e. the “Bohr radius”, the equation (390) takes the form
2𝑍𝑟 1 (391)
𝜌= .
𝑛 𝑎0
So that
𝑛𝑎0 (392)
𝑟= 𝜌
2𝑍
Also
𝑛𝑎0 (393)
𝑑𝑟 = 𝑑𝜌
2𝑍
After using the values of 𝑅𝑛,𝑙 (𝜌), r and dr from equation (388, 392, 393) in equation (389), we get
∞
𝑛𝑎0 2 𝑛𝑎0 (394)
2
𝐶 ∫ 𝑒 𝜌 . 𝜌2𝑙 . [𝐿2𝑙+1
2
𝑛+𝑙 (𝜌)] . [ 𝜌] . [ ] 𝑑𝜌 = 1
2𝑍 2𝑍
0
or
no watermark.
2
𝑛𝑎0 3 2𝑛{(𝑛 + 𝑙)!}3 (395)
𝐶 ( ) [ ]=1
2𝑍 (𝑛 − 𝑙 − 1)!
or
(395)
2𝑍 3 (𝑛 − 𝑙 − 1)!
𝐶 = √( ) [ ]
𝑛𝑎0 2𝑛{(𝑛 + 𝑙)!}3
After using the value of normalization constant from above equation into equation (388), we get
𝑘=𝑛−𝑙−1 (396)
2𝑍 3 (𝑛 − 𝑙 − 1)! (−1)𝑘+1 [(𝑛 + 𝑙)!]2 𝜌𝑘
𝑅𝑛,𝑙 (𝜌) = √( ) [ ] 𝑒 −𝜌/2 𝜌𝑙 ∑
𝑛𝑎0 2𝑛{(𝑛 + 𝑙)!}3 (𝑛 − 𝑙 − 1 − 𝑘)! (2𝑙 + 1 + 𝑘)! 𝑘!
𝑘=0
2𝑍𝑟 𝑘 (397)
2𝑍 3
(𝑛 − 𝑙 − 1)! 𝑍𝑟 2𝑍𝑟 𝑙 𝑘=𝑛−𝑙−1 (−1)𝑘+1 [(𝑛 + 𝑙)!]2 ( )
𝑛𝑎0
= √( ) [ 3
] . exp (− ).( ) . ∑
𝑛𝑎0 2𝑛{(𝑛 + 𝑙)!} 𝑛𝑎0 𝑛𝑎0 (𝑛 − 𝑙 − 1 − 𝑘)! (2𝑙 + 1 + 𝑘)! 𝑘!
𝑘=0
Which is the complete solution of R-equation.
Table 3. Some of the initial radial wave functions in terms of distance from the center of the nucleus for
the hydrogen atom and other hydrogen-like species.
n l Radial wave function (𝑅𝑛,𝑙 )
1 0 𝑍 3/2 −𝑍𝑟/𝑎
𝑅1,0 = 2( ) 𝑒 0
𝑎0
2 0 1 𝑍 3/2 𝑍𝑟
𝑅2,0 = ) (2 − ) 𝑒 −𝑍𝑟/2𝑎0
(
2√2 𝑎0 𝑎0
2 1 𝑍 3/2 𝑍𝑟 −𝑍𝑟/2𝑎
1
𝑅2,1 = (
) ( )𝑒 0
2√6 𝑎0 𝑎0
3 0 2 𝑍 3/2 𝑍𝑟 𝑍𝑟 2
𝑅3,0 = ( ) (27 − 18 − 2 ( ) ) 𝑒 −𝑍𝑟/3𝑎0
81√3 𝑎0 𝑎0 𝑎0
3 1 4 𝑍 3/2 𝑍𝑟 𝑍𝑟 2
𝑅3,1 = ( ) (6 ( ) − ( ) ) 𝑒 −𝑍𝑟/3𝑎0
81√6 𝑎0 𝑎0 𝑎0
3 2 1 𝑍 3/2 𝑍𝑟 3/2 𝑍𝑟 2
𝑅3,2 = ) ( ) − ( ) 𝑒 −𝑍𝑟/3𝑎0
(
81√30 𝑎0 𝑎0 𝑎0
no watermark.
The total wavefunction: After solving the ϕ-, θ- and r-dependent equations, we have Φm(ϕ), Θl,m(θ) and Rn,l(r)
functions. Now, recall the total wave function that depends upon all the three variable i.e.
𝜓𝑛,𝑙,𝑚 (𝑟, 𝜃, 𝜙) = 𝜓𝑛,𝑙 (𝑟) × 𝜓𝑙,𝑚 (𝜃) × 𝜓𝑚 (𝜙) (398)
After putting the values of Φm(ϕ), Θl,m(θ) and Rn,l(r) from equation (397) in equation (398), we get
𝜓𝑛,𝑙,𝑚 (𝑟, 𝜃, 𝜙) = 𝑅𝑛,𝑙 . 𝛩𝑙,𝑚 . 𝛷𝑚 (399)
2𝑍𝑟 𝑘 (400)
𝑙 𝑘=𝑛−𝑙−1 (−1)𝑘+1 [(𝑛 + 𝑙)!]2 (
𝑛𝑎0 )
3
2𝑍 (𝑛 − 𝑙 − 1)! 𝑍𝑟 2𝑍𝑟
= √( ) [ 3
] . exp (− ).( ) . ∑
𝑘=0
(2𝑙 + 1)(𝑙 − 𝑚)! 𝑚 1

×√ . 𝑃𝑙 (𝐶𝑜𝑠 𝜃) × √ 𝑒 𝑖𝑚𝜙
2(𝑙 + 𝑚)! 2𝜋
Which is the complete expression for all the quantum mechanical states of a single electron around the nucleus.
Table 4. Some of the initial total wave functions for the hydrogen atom and other hydrogen-like species.
n l m Total wave function (𝜓𝑛,𝑙,𝑚 )
1 0 0 1 𝑍 3/2 −𝑍𝑟/𝑎
𝜓1,0,0 = ( ) 𝑒 0
√𝜋 𝑎0
2 0 0 1 𝑍 3/2 𝑍𝑟
𝜓2,0,0 = ( ) (2 − ) 𝑒 −𝑍𝑟/2𝑎0
4√𝜋 𝑎0 𝑎0
2 1 0 1 𝑍 5/2
𝜓2,1,0 = ( ) 𝑒 −𝑍𝑟/2𝑎0 𝑟 𝐶𝑜𝑠𝜃
4√𝜋 𝑎0
2 1 ±1 1 𝑍 5/2 −𝑍𝑟/2𝑎
𝜓2,1,±1 = ( ) 𝑒 0 𝑆𝑖𝑛𝜃 𝑒 −𝑖𝜙
4√𝜋 𝑎0
3 0 0 2𝑍 3/2 𝑍𝑟 𝑍𝑟 2 1
𝜓3,0,0 = ( ) (27 − 18 − 2 ( ) ) 𝑒 −𝑍𝑟/3𝑎0 .
81√3 𝑎0 𝑎0 𝑎0 √4𝜋
3 1 0
4𝑍 3/2 𝑍𝑟 𝑍𝑟 2 3 1
𝜓3,1,0 = ( ) (6 ( ) − ( ) ) 𝑒 −𝑍𝑟/3𝑎0 . √ 𝐶𝑜𝑠 𝜃.
81√6 𝑎0 𝑎0 𝑎0 2 √2𝜋
3 1 ±1
4𝑍 3/2 𝑍𝑟 𝑍𝑟 2 3 1
𝜓3,1,±1 = ( ) (6 ( ) − ( ) ) 𝑒 −𝑍𝑟/3𝑎0 . √ 𝑆𝑖𝑛 𝜃. √ 𝑒 ±𝑖𝜙
81√6 𝑎0 𝑎0 𝑎0 2 2𝜋
no watermark.
The eigenvalues of energy: Since the series 𝐺(𝜌) consists of infinite number of terms, the function 𝐹(𝜌)
becomes infinite at a very large value of k i.e. infinite. Consequently, the function 𝑅(𝜌) will also become
infinite if the number of terms are not limited to a finite value. Therefore, we must break off the series to a
finite number of terms which is possible only if the numerator in equation (381) becomes zero i.e.
𝑙+1−𝜆+𝑘 =0 (401)
or
𝜆 =𝑙+1+𝑘 =𝑛 (402)
Where n is the principal quantum number and can have values 1, 2, 3. 4 …. because l and k are integers always.
Now recall the value of λ from equation (338) and then squaring both sides, we get
𝜇2 𝑍 2 𝑒 4 (403)
𝜆2 =
ħ4 𝛼 2
Also putting the value of 𝛼 2 from equation (338) in equation (403), we get
𝜇2 𝑍 2 𝑒 4 𝜇 2 𝑍 2 𝑒 4 ħ2 𝜇𝑍 2 𝑒 4 (404)
𝜆2 = = − . = −
ħ4 𝛼 2 ħ4 2𝜇𝐸 2 𝐸 ħ2
𝜇𝑍 2 𝑒 4 𝜇𝑍 2 𝑒 4 (405)
𝐸𝑛 = − == −
2 𝜆2 ħ2 2 𝑛 2 ħ2
Which is the same as given by the pre-wave-mechanical quantum theory.
Figure 14. The energy level for various quantum mechanical states of the hydrogen atom.
It is also worthy to note that the total number of wave functions that can be written for a given value of n are
n2, and therefore, we can say that the degeneracy of any energy level is also n2.
no watermark.
 Principal, Azimuthal and Magnetic Quantum Numbers and the Magnitude

of Their Values
The Schrodinger wave equation for hydrogen and hydrogen-like species in the polar coordinates can
be written as:
1 𝜕 2 𝜕𝜓 1 𝜕 𝜕𝜓 1 𝜕2𝜓 8𝜋 2 𝜇 𝑍𝑒 2 (406)
[ (𝑟 ) + (𝑆𝑖𝑛𝜃 ) + ] + (𝐸 + )𝜓 = 0
𝑟 2 𝜕𝑟 𝜕𝑟 𝑆𝑖𝑛𝜃 𝜕𝜃 𝜕𝜃 𝑆𝑖𝑛2 𝜃 𝜕𝜙 2 ℎ2 𝑟
After separating the variables present in the equation given above, the solution of the differential equation was
found to be
𝜓𝑛,𝑙,𝑚 (𝑟, 𝜃, 𝜙) = 𝑅𝑛,𝑙 . 𝛩𝑙,𝑚 . 𝛷𝑚 (407)
2𝑍𝑟 𝑘 (408)
𝑙 𝑘=𝑛−𝑙−1 (−1)𝑘+1 [(𝑛 + 𝑙)!]2 (
𝑛𝑎0 )
3
2𝑍 (𝑛 − 𝑙 − 1)! 𝑍𝑟 2𝑍𝑟
= √( ) [ 3
] . exp (− ).( ) . ∑
𝑘=0
(2𝑙 + 1)(𝑙 − 𝑚)! 𝑚 1

×√ . 𝑃𝑙 (𝐶𝑜𝑠 𝜃) × √ 𝑒 𝑖𝑚𝜙
2(𝑙 + 𝑚)! 2𝜋
It is obvious that the solution of equation (406) contains three discrete (n, l, m) and three continuous (r, θ, ϕ)
variables. In order to be a well-behaved function, there are some conditions over the values of discrete variables
that must be followed i.e. boundary conditions. Therefore, we can conclude that principal (n), azimuthal (l)
and magnetic (m) quantum numbers are obtained as a solution of the Schrodinger wave equation for hydrogen
atom; and these quantum numbers are used to define various quantum mechanical states. In this section, we
will discuss the properties and significance of all these three quantum numbers one by one.
 Principal Quantum Number
The principal quantum number is denoted by the symbol n; and can have value 1, 2, 3, 4, 5…..∞. The
label “principal” is allotted because valid values of l and m can be defined only after defining an acceptable
value of n. Some of the most important significances of the principal quantum number are given below.
1. The energy of an electron in hydrogen-like systems: The principal quantum number gives the energy of
the electron in all hydrogen and hydrogen-like species by the following relation.
𝜇𝑍 2 𝑒 4 (409)
𝐸𝑛 = −
2 𝑛 2 ħ2
Where μ is the reduced mass of the system while e represents the electronic charge. The symbol Z represents
the nuclear charge of the one-electron system. Now since main shells are nothing but the classification of
different quantum mechanical states of electron on the basis of energy only, we can also say that n tells about
the main shells in the modern wave mechanical model of the atom.

2. Degeneracy in hydrogen-like systems: Since the total number of wave functions that can be written for a
given value of n are n2, we can say that the degeneracy of any energy level is also n2. In other words, we can
say that because the energy depends only upon the value of n, all wave functions with the same value of n must
possess the same energy. For instance, if we 𝑛 = 2, a total of four wave-functions can be written i.e.
𝜓2,0,0 , 𝜓2,1,0 , 𝜓2,1,+1 and 𝜓2,1,−1 . Owing to the same value of n, all of these states are bound to have the same
energy, and thus, are degenerate.
3. The maximum number of electrons per unit cell: Since two electrons can have the same set of principal,
orbital and magnetic quantum numbers via opposite spins, the maximum number of electrons per unit cell will
be 2n2 i.e. the double of the degeneracy. For instance, if we 𝑛 = 2, the maximum number of electrons that can
be filled in the second main shell is 2 × 22 = 8. Similarly, if we 𝑛 = 3, the maximum number of electrons
that can be filled in the third main shell is 2 × 32 = 18.
4. Spectra of elemental hydrogen: In order to understand this concept, recall the energy expression for the
hydrogen atom i.e.
𝑚 𝑒4 4𝜋 2 𝑚 𝑒 4 (410)
𝐸𝑛 = − = −
2 𝑛2 ħ2 2 𝑛2 ℎ2
In the SI system, the above equation needs to be corrected for permittivity factor (4πεo) i.e.
4𝜋 2 𝑚 𝑒 4 4𝜋 2 𝑚 𝑒 4 (411)
𝐸𝑛 = − 𝐽𝑜𝑢𝑙𝑒𝑠 = − 𝐽𝑜𝑢𝑙𝑒𝑠
2 𝑛2 ℎ2 (4𝜋𝜀𝑜 )2 32 𝜋 2 𝑛2 ℎ2 𝜀𝑜2
or
𝑚 𝑒4 (412)
𝐸𝑛 = − 𝐽𝑜𝑢𝑙𝑒𝑠
8 𝑛2 ℎ2 𝜀𝑜2
Converting Joules into cm−1 (dividing by hc) the above equation takes the form
𝑚 𝑒4 𝑅 (413)
𝜈̅𝑛 = − 2 3 2 𝑐𝑚−1 = − 2 𝑐𝑚−1
8 𝑛 ℎ 𝑐 𝜀𝑜 𝑛
Now the selection rules for electronic transitions are
𝛥𝑛 = 𝑎𝑛𝑦𝑡ℎ𝑖𝑛𝑔 𝑎𝑛𝑑 𝛥𝑙 = ±1 (414)
This means that electron can move from s to p-orbital only; and all s–s, p–p, d–d and f–f transitions are Laporte
forbidden. Now assume that electron shows a transition from an initial quantum mechanical state (n1) to the
final quantum mechanical state (n2). The energy of absorption can be formulated as:
𝑅 𝑅 −1
(415)
𝛥𝜈̅ = 𝜈̅𝑛2 − 𝜈̅𝑛1 = (− 2 ) − (− 2 ) 𝑐𝑚
𝑛2 𝑛1
or
no watermark.
1 1 −1
(416)
𝛥𝜈̅ = 𝑅 ( 2 − 2 ) 𝑐𝑚
𝑛1 𝑛2
The above equation can also be used to determine the wavenumber of the emission spectral line of the hydrogen
atom. All the possibilities and corresponding series are given below.
Figure 15. Energy level diagram of the hydrogen atom in the units of Rydberg constant.
At this stage, we must consider all the possibilities that may arise from the transitioning of the electron from
different quantum mechanical states. These transitions are grouped in various series labeled as Lyman, Balmer,
Paschen, Brackett and Pfund series.
Table 5. Different spectral series in the hydrogen atom.
Series name Lower state (n1) Higher state (n2) Region
Lyman 1 2, 3, 4, 5, …. ∞ UV
Balmer 2 3, 4, 5, 6, …. ∞ Visible
Paschen 3 4, 5, 6, 7, …. ∞ Near IR
Brackett 4 5, 6, 7, 8, …. ∞ Mid IR
Pfund 5 6, 7, 8, 9, …. ∞ Far IR
no watermark.
 Azimuthal Quantum Number

The azimuthal quantum number is denoted by the symbol l; and can have value n–1, n–2, n–3…..0.
The label azimuthal quantum number is also called as “angular momentum quantum number” because the
values of l also govern the orbital angular momentum of the electron in a particular quantum mechanical state.
Some of the most important significances of the principal quantum number are given below.
1. Orbital angular momentum of the electron: The azimuthal quantum number gives the angular momentum
of the electron in all hydrogen and hydrogen-like species by the following relation.
(417)
< 𝐿 >= ∮ 𝜓𝑛,𝑙,𝑚 (𝑟, 𝜃, 𝜙) 𝐿̂ 𝜓𝑛,𝑙,𝑚 (𝑟, 𝜃, 𝜙)
ℎ (418)
= √𝑙(𝑙 + 1)
2𝜋
After looking at the equation (418), it is obvious that it’s only the ‘l’ quantum number that controls the
magnitude of the orbital angular momentum quantum number. Furthermore, owing to the quantized nature of
‘l’ quantum number, the angular momentum of an electron in an atom is also quantized. For instance, if we
use l = 0, 1, 2, 3 in equation (418), we will get 0, √2, √6 and √12 units of angular momentum, respectively.
2. Subshells in the main shell: The azimuthal quantum number can also be used to classify different quantum
mechanical states on the basis of orbital angular momentum. In other words, subshells are nothing but the
classification degenerate quantum mechanical states on the basis of angular momentum.
Figure 16. Energy level diagram of the hydrogen atom with further classification.
no watermark.
3. Shape and number of angular nodes in atomic orbital: The angular momentum quantum number, l, also
controls the number of angular nodes that pass through the nucleus. An angular node (planar or conical) is
observed when the angular part of the wave function passes through zero and changes sign.
Figure 17. Different orbitals and the corresponding angular nodes.
4. The energy of different subshells in multi-electron atoms: In hydrogen and H-like atoms (i.e. one-
electron systems), the energy levels depend only upon the principal quantum number. However, these energy
levels also split according to the magnitude of l as well. Quantum states of higher l are placed above than the
states with lower l. For instance, the energy of 2s orbital is lower than 2p, 3d exists at higher position than 3p.
Figure 18. The energy pattern of different subshells in multi-electron atoms.
no watermark.
 Magnetic Quantum Number

The magnetic quantum number is denoted by the symbol m, and can have values +l to –l in unit steps.
In other words, the quantum number m is nothing but the allowed effects of orbital angular momentum in the
z-direction. The label “magnetic quantum number” arises because m affects the energy of the electron in an
externally applied magnetic field. In the absence of such a field, all spherical harmonics corresponding to the
different arbitrary values of m will be equivalent. Some of the most important significances of the principal
quantum number are given below.
1. The orientation of orbital angular momentum: The azimuthal quantum number gives the angular
momentum of the electron in all hydrogen and hydrogen-like species by the following relation:
ℎ (419)
𝐿𝑙 = √𝑙(𝑙 + 1)
2𝜋
Since 𝑙 = 0, 1, 2, 3, 4 … … (𝑛 − 1) etc., the quantum mechanically allowed values of orbital angular momentum
(in the units of ℎ/2𝜋) are given below.
𝐿0 = √0(0 + 1) unit = 0 unit (420)
𝐿1 = √1(1 + 1) unit = √2 unit (421)
𝐿2 = √2(2 + 1) unit = √6 unit (422)
𝐿3 = √3(3 + 1) unit = √12 unit (423)
However, there is boundary condition in quantum mechanics that says that only integral effects are allowed
reference direction if the angular momentum is generated by integral quantum number and half-integral effects
are allowed in reference direction if the momentum is generated by half-integral quantum number.
Since, 𝐿𝑧 = 𝐿 𝐶𝑜𝑠 𝜃, √2 units of orbital angular momentum cannot orient itself along z-axis because
this makes 𝜃 = 0°, and since 𝐶𝑜𝑠 0 = 1, 𝐿⃗𝑧 = 𝐿 i.e. orbital angular momentum effect along the z-axis is also
1.414 unit which is not allowed quantum mechanically. The effects of angular momentum allowed in the z-
direction are +1, 0, −1; for which angles required are determined as follows.
1 (424)
+1 = √2 𝐶𝑜𝑠 𝜃 ⇒ 𝜃 = 𝐶𝑜𝑠 −1 = 45°
√2
0 (425)
0 = √2 𝐶𝑜𝑠 𝜃 ⇒ 𝜃 = 𝐶𝑜𝑠 −1 = 90°
√2
−1 (426)
−1 = √2 𝐶𝑜𝑠 𝜃 ⇒ 𝜃 = 𝐶𝑜𝑠 −1 = 135°
√2
no watermark.
Hence, we can say that in order to be allowed, the 1.414 units of orbital angular momentum must orient itself
only at 45°, 90° and 135° in space from reference direction (z-axis in this case). Since the orientation of angular
momentum can orient itself in any direction from the z-axis as far as the effective orbital angular momentum
+1 unit along z-direction; therefore, we should use a cone around the same at 45°. The same is true for 0 and
−1 effects with 90° and 135°, respectively.
Figure 19. The space quantization of orbital angular momentum of an electron for l = 0, 1, 2 and 3 states.
It is also worthy to mention that all the orientations of orbital angular momentum are degenerate in the absence
of any externally applied magnetic field.
no watermark.
2. The energy of different orientations: The probability of different orientations of orbital angular
momentum, and also the corresponding magnetic fields, are same. However, after applying the magnetic field
along the z-direction, the situation will not be the same.
The orientation with a maximum negative value of orbital angular momentum along the z-axis will
have magnetic dipole aligned along the applied magnetic field, and thus, will be most stable. Conversely, the
orientations with the maximum positive value of orbital angular momentum along the z-axis will have
magnetic dipole aligned opposite to the applied magnetic field, and thus, will be least stable. Likewise, the
orientations with angular momentum component in between will also have intermediary energies in this case.
Figure 20. Different orientations of the orbital angular momentum of an electron in a d-subshell and
corresponding energies in the applied magnetic field.
To understand this, consider the typical case of d-subshell. The orbital angular momentum for the
corresponding electron can be obtained using equation (419) i.e.
ℎ (427)
𝐿 = √2(2 + 1)
2𝜋
ℎ (428)
𝐿 = √6
2𝜋
The allowed effects of orbital angular momentum in the z-direction are +2, +1, 0, −1, −2 in the units of h/2π.
Therefore, each spectral line arising from the transition to the d-subshell will split in a quintet in the presence
of the externally applied magnetic field.
no watermark.
 Probability Distribution Function

The probability distribution function is the behavior of ψ2 at various points around the nucleus as a
function of distance r from the nucleus. The plots of such functions are also called as the probability
distribution curves. Nevertheless, since it is only the radial part (𝑅𝑛,𝑙 ) that varies with the distance from the
nucleus, the graphs of ψ2 must behave in the same manner. To understand this more precisely, consider the
plot of the first two quantum mechanical states of an electron in a hydrogen atom.
 Probability Distribution of 𝝍𝟏,𝟎,𝟎 State (1s Orbital)
In order to understand the probability distribution function of the electron in the ground state of the
hydrogen atom, recall the mathematical expression for the same i.e.
1 1 3/2 −𝑟/𝑎 (429)

𝜓1,0,0 = ( ) 𝑒 0
√𝜋 𝑎0
Squaring both sides, we get
2
1 −2𝑟/𝑎 (430)
𝜓1,0,0 = 𝑒 0
𝜋𝑎03
It is obvious from the equation (429, 430) that the pre-exponential part is simply a constant and variation
depends only upon the exponential part.
Figure 21. The variation of electron density vs distance from the center of the nucleus in 1s orbital.
Hence, it can be concluded that the density of the electron wave is highest at the center of the nucleus and
decreases as the distance from the center of the nucleus increases, and becomes zero only at infinite.

 Probability Distribution of 𝝍𝟐,𝟎,𝟎 State (2s Orbital)

In order to understand the probability distribution function of an electron in the 2s state of the
hydrogen atom, recall the mathematical expression for the same i.e.
1 1 3/2 𝑟 (431)
𝜓2,0,0 = ( ) (2 − ) 𝑒 −𝑟/2𝑎0
4√𝜋 𝑎0 𝑎0
Squaring both sides, we get
2
1 𝑟 2 −𝑟/𝑎 (432)
𝜓2,0,0 = (2 − ) 𝑒 0
16𝜋𝑎03 𝑎0
It is obvious from the equation (431, 432) that the pre-exponential part is simply a constant and variation
depends only upon the exponential part.
Figure 22. The variation of electron density vs distance from the center of the nucleus in 2s orbital.
Hence, it can be concluded that the density of electron wave is non zero at the center of the nucleus and
decreases as the distance from the center of the nucleus increases, and becomes zero at 𝑟 = 2𝑎0 . Now since
the wave function changes sign after 2𝑎0 , the density of electron wave after that increases first and then
decreases exponentially and finally becomes zero at infinite distance. Now it’s quite confusing because we
have been told that the electron cannot reside within the nucleus and the probability of finding the electron
inside the nucleus is almost zero, meaning that there must be something else that also governs the probability.
no watermark.
 Radial Distribution Function

The radial distribution function is the behavior of 𝑅𝑛,𝑙
2
. 4𝜋𝑟 2 𝑑𝑟 as a function of distance r from the
center of the nucleus. These plots solve the problem posed by the simple “probability distribution curves”
which suggested that the probability of finding the electron must be highest at the center of the nucleus in the
ground electronic state. In the radial distribution plots, we assume that the probability of finding the particle at
a distance r from the nucleus depends not only upon the density of electron wave but also varies with the
magnitude of the volume of the spherical shell of dr thickness at the same distance. This is quite rational
because the r can be in any direction around the nucleus.
Consider that the space around the nucleus is divided into an infinite number of concentric shells of
thickness dr. Now though the electron density will show a decrease with increasing r, the volume of the
concentric shells will increase. More volume at distance r means more the chances of finding the electron at
same. The two effects will try to counter each other, and therefore, the resultant probability at distance r must
be the multiplication of the two effects i.e.
2
𝑅𝑎𝑑𝑖𝑎𝑙 𝑝𝑟𝑜𝑏𝑎𝑏𝑖𝑙𝑖𝑡𝑦 = 𝜓𝑛,𝑙,𝑚 × 𝑑𝑉𝑠ℎ𝑒𝑙𝑙 (433)
Nevertheless, since it is only the radial part (𝑅𝑛,𝑙 ) that varies with the distance from the nucleus, the above
expression for simplicity can be reduced to
2
𝑅𝑎𝑑𝑖𝑎𝑙 𝑝𝑟𝑜𝑏𝑎𝑏𝑖𝑙𝑖𝑡𝑦 = 𝑅𝑛,𝑙 × 𝑑𝑉𝑠ℎ𝑒𝑙𝑙 (434)
Now as we have already derived the mathematical expression of radial wavefunction hydrogen atom already
in this previously, the only thing we need is the mathematical expression of the volume element also.
Figure 23. The depiction of a concentric shell of thickness dr around the nucleus of a hydrogen atom at a
distance r.

The volume of the shaded portion (spherical shell of thickness dr) can be obtained subtracting the volume of
the inner sphere from the outer sphere i.e.
4 4 (435)
𝑑𝑉 = 𝜋(𝑟 + 𝑑𝑟)3 − 𝜋𝑟 3
3 3
4 4 (436)
= 𝜋(𝑟 3 + 𝑑𝑟 3 + 3𝑟 2 𝑑𝑟 + 3𝑟 𝑑𝑟 2 ) − 𝜋𝑟 3
3 3
4 4 4 (437)
= 𝜋𝑟 3 + 𝜋𝑑𝑟 3 + 4𝜋𝑟 2 𝑑𝑟 + 4𝜋𝑟 𝑑𝑟 2 − 𝜋𝑟 3
3 3 3
4 (438)
𝑑𝑉 = 𝜋𝑑𝑟 3 + 4𝜋𝑟 2 𝑑𝑟 + 4𝜋𝑟 𝑑𝑟 2
3
Since dr is very small, the terms involving square and cube of dr can be neglected for simplicity. All this leaves
us with only one term i.e. 𝑑𝑉 = 4𝜋𝑟 2 𝑑𝑟. After using the value of dV in equation (434), we get
2
𝑅𝑎𝑑𝑖𝑎𝑙 𝑝𝑟𝑜𝑏𝑎𝑏𝑖𝑙𝑖𝑡𝑦 = 𝑅𝑛,𝑙 × 4𝜋𝑟 2 𝑑𝑟 (439)
To understand this more precisely, consider the plot for the ground quantum mechanical state of an electron in
a hydrogen atom i.e. 1s orbital.
 Radial Probability Distribution Curve for Ground State of Hydrogen Atom
The valid values of n, l and m that can be put in the general form of the hydrogenic wavefunction to
obtain ground state are 1, 0 and 0, respectively. Therefore, we can start by writing the mathematical expression
for the same i.e.
1 3/2 −𝑟/𝑎 (440)

𝑅1,0 = 2 ( ) 𝑒 0
𝑎0
The probability distribution function can be obtained by squaring equation (440) i.e.
2
4 −2𝑟/𝑎 (441)
𝑅1,0 = 𝑒 0
𝑎03
After multiplying the “probability distribution function” with “volume element”, the expression for the “radial
distribution function” can be formulated. Mathematically, we can say that
4 −2𝑟/𝑎
0 × 4𝜋𝑟 2 𝑑𝑟
(442)
𝑃(𝑟) = 𝑒
𝑎03
It is obvious from the equation (442) that probability will become zero if we put r = 0 (4𝜋𝑟 2 𝑑𝑟 = 0). Now, if
we increase the r, the radial probability will first increase due to increasing volume element, attaining maxima;
and then it will start declining due to the dominance of 𝑅1,0 2
part. In other words, the density of electron-wave
decreases exponentially but the volume of the concentric shell increases continuously.
no watermark.
Figure 24. The variation of radial probability as a function of r (1s orbital).
In order to find the radius of maximum probability, we need to put 𝑑𝑃/𝑑𝑟 equal to zero. It has been found that
the radius of maximum probability will come out to be 0.53×10−10 m, which is exactly equal to the radius of
the first Bohr orbit (a0).
 Radial Probability Distribution Curves for Other Hydrogenic Wavefunctions
The other valid sets of n, l can be put in the general form of radial part of the wavefunction, to obtain
2
𝑅𝑛,𝑙 , and hence the corresponding “radial distribution functions”.
Figure 25. The variation of radial probability as a function of distance from the center of the nucleus.
no watermark.
 Shape of Atomic Orbitals (s, p & d)

The wave mechanical model of atom says that there is a non-zero probability of finding the electron
almost everywhere in space excepting the angular and radial nodes. This means that primitive diagrams that
depict the orbital shapes are intended to describe the region encompassing 90−95% probability density. In a
typical drawing of orbital, we first plot the radial wave function and the angular part is superimposed. The
shapes of some typical orbitals are discussed below.
 Shape of s-Orbitals
In order to draw the shape of s-orbital, we first need to recall the radial part of the same and then we
will have to superimpose the angular part. For instance, the radial part of 1s orbital is
1 3/2 −𝑟/𝑎 (443)

𝑅1,0 = 2 ( ) 𝑒 0
𝑎0
It is obvious from the equation (443) that the radial part of the wave function has the largest magnitude when
r = 0, and it decreases as we move away from the nucleus. The function will become zero only at infinite
distance and will never change its sign. All this leads to a spherical-shaped cloud without any radial node. The
angular part of every s-orbital is
1 (444)
𝛶0,0 = = 0.28
√4𝜋
Hence, after multiplying radial wave function by a constant value of the angular part, the magnitude of function
at all the points in space will reduce to 28% of the initial value.
Figure 26. The shape of some lower energy s-orbitals.
Similarly, the shapes of some other s-orbitals are also given below to explain the concept more precisely. It is
worthy to mention that the plots are easy to draw if we treat radial and angular parts consequently.

 Shape of p-Orbitals
In order to draw the shape of p-orbital, we first need to recall the radial part of the same and then we
will have to superimpose the angular part. For instance, the radial part of 2p orbital is
1 1 3/2 𝑟 (445)
𝑅2,1 = ( ) ( ) 𝑒 −𝑟/2𝑎0
2√6 𝑎0 𝑎0
It is obvious from the equation (445) that the radial part of the wave function has the zero magnitudes when r
= 0; and it increases as we move away from the nucleus, reaches a maximum, and decreases afterward. The
function becomes zero only at infinite distance and will never change its sign. All this leads to a spherical-
shaped cloud without any radial node. The angular part of p-orbitals are
(446)
3 1
𝛶1,0 = √ 𝐶𝑜𝑠 𝜃.
2 √2𝜋
(447)
3 1
𝛶1,±1 = √ 𝑆𝑖𝑛 𝜃. √ 𝑒 ±𝑖𝜙
2 2𝜋
Hence, the full plot for pz-orbital is obtained after multiplying radial wave function by angular part given by
equation (446); and the sign of function above the xy-plane will remain positive whereas a negative sign will
be obtained below xy-plane. Similarly, we can obtain the three-dimensional plots for px and py by multiplying
equation (445) by equation (447).
Figure 27. The shape of 2p-orbitals.
Similarly, the shapes of some other p-orbitals are also given below to explain the concept more precisely. It is
no watermark.
Figure 28. The shape of some 3p, 4p and 5p orbitals.
no watermark.
 Shape of d-Orbitals
In order to draw the shape of d-orbital, we first need to recall the radial part of the same and then we
will have to superimpose the angular part. For instance, the radial part of 3d orbital is
1 𝑍 3/2 𝑍𝑟 3/2 𝑍𝑟 2 (448)

𝑅3,2 = ( ) ( ) − ( ) 𝑒 −𝑍𝑟/3𝑎0
81√30 𝑎0 𝑎0 𝑎0
It is obvious from the equation (448) that the radial part of the wave function has the zero magnitudes when r
= 0; and it increases as we move away from the nucleus, reaches a maximum, and decreases afterward. The
function becomes zero only at infinite distance and will never change its sign. All this leads to a spherical-
shaped cloud without any radial node. The angular part of d-orbitals are
(449)
5 1
𝛶2,0 = √ (3𝐶𝑜𝑠 2 𝜃 − 1).
8 √2𝜋
(450)
15 1
𝛶2,±1 = √ 𝑆𝑖𝑛 𝜃 𝐶𝑜𝑠 𝜃. √ 𝑒 ±𝑖𝜙
4 2𝜋
(451)
15 1
𝛶2,±2 = √ 𝑆𝑖𝑛2 𝜃. √ 𝑒 ±𝑖2𝜙
16 2𝜋
Hence, the full plot for dz2-orbital is obtained after multiplying radial wave function by angular part given by
equation (449); and the sign of function in the xy-plane will become negative whereas a positive sign will be
obtained in two opposite lobes along z-axis. It is also worthy to note that the function becomes completely zero
in two conical surfaces (above and below) before changing its sign. Similarly, we can obtain the three-
dimensional plots for px and py by multiplying equation (448) by equation (450, 451).
Figure 29. Continued on the next page…
no watermark.
Figure 29. The shape of 3d-orbitals.
Similarly, the shapes of some other d-orbitals are also given below to explain the concept more precisely. It is
Figure 30. The shape of 4d orbitals.
no watermark.
It is also worthy to mention that the radii of maximum probability for 4d orbitals are larger than that
of 3d orbitals. The same is true for s and p orbitals i.e. radius of maximum probability of s and p orbitals follow
the order 3s > 2s > 1s and 4p > 3p > 2p, respectively.
no watermark.
 Problems
Q 1. Derive and discuss the Schrodinger wave equation for a particle of mass m trapped inside a cubical box
with side a. Provided that the potential inside the box is zero while outside the box is infinite.
Q 2. Discuss the concept of the degeneracy of quantum mechanical states in a 3D box.
Q 3. What is the zero-point energy of a simple harmonic oscillator? How does it vary with force constant?
Q 4. Derive and discuss the Schrodinger wave equation for a diatomic rigid rotator. Also, draw the energy
level diagram for the same.
Q 5. Define space quantization with special reference to diatomic rigid rotator.
Q 6. What is the difference between the radial and angular wave function for hydrogen atom? Write down both
parts for 3dz2 orbital.
Q 7. What are quantum numbers in the modern wave mechanical model of the atom? Also, discuss the main
significance of the principal quantum number.
Q 8. Write down a short note on “probability distribution functions”.
Q 9. What are “radial distribution functions”? Also, explain how you would determine the radius of maximum
probability for 1s orbital of the hydrogen atom.
Q 10. What are the formulas to find the number of angular and radial nodes?
Q 11. Draw and discuss the shape of 4dxy and 3dz2 in detail

 Bibliography
[1] B. R. Puri, L. R. Sharma, M.S. Pathania, Principles of Physical Chemistry, Vishal Publications, Jalandhar,
India, 2018.
[2] M. Reed, B. Simon Functional Analysis, Elsevier, Amsterdam, Netherlands, 2003.
[3] G. E. Bowman, Essential Quantum Mechanics, Oxford University Press, Oxford, UK, 2008.
[4] W. Heisenberg, Über den anschaulichen Inhalt der quantentheoretischen Kinematik und Mechanik,
Zeitschrift für Physik, 1927, 172.
[5] E. Schrödinger, Die gegenwärtige Situation in der Quantenmechanik, Naturwissenschaften. 1935, 807.
[6] P. Alberto, C. Fiolhaisdag, V. Gil, Relativistic particle in a box, European Journal of Physics, 1996, 17.
[7] R. K. Prasad, Quantum Chemistry, New Age International Publishers, New Delhi, India, 2010.
[8] I. N. Levine, Quantum Chemistry, Pearson Prentice Hall, New Jersey, USA, 2009.
[9] D. A. McQuarrie, Quantum Chemistry, University Science Books, California, USA, 2008.
[10] E. Steiner, The Chemistry Maths Book, Oxford University Press, Oxford, UK, 2008.
[11] P. Atkins, J. Paula, Physical Chemistry, Oxford University Press, Oxford, UK, 2010.

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Table of Contents
CHAPTER 1 ................................................................................................................................................ 11
Quantum Mechanics – I ........................................................................................................................ 11
 Postulates of Quantum Mechanics .................................................................................................. 11
 Derivation of Schrodinger Wave Equation...................................................................................... 16
 Max-Born Interpretation of Wave Functions .................................................................................. 21
 The Heisenberg’s Uncertainty Principle.......................................................................................... 24
 Quantum Mechanical Operators and Their Commutation Relations............................................... 29
 Hermitian Operators – Elementary Ideas, Quantum Mechanical Operator for Linear Momentum,
Angular Momentum and Energy as Hermitian Operator ................................................................. 52
 The Average Value of the Square of Hermitian Operators ............................................................. 62
 Commuting Operators and Uncertainty Principle (x & p; E & t) .................................................... 63
 Schrodinger Wave Equation for a Particle in One Dimensional Box.............................................. 65
 Evaluation of Average Position, Average Momentum and Determination of Uncertainty in Position
and Momentum and Hence Heisenberg’s Uncertainty Principle..................................................... 70
 Pictorial Representation of the Wave Equation of a Particle in One Dimensional Box and Its
Influence on the Kinetic Energy of the Particle in Each Successive Quantum Level ..................... 75
 Lowest Energy of the Particle ......................................................................................................... 80
 Problems .......................................................................................................................................... 82
 Bibliography .................................................................................................................................... 83
CHAPTER 2 ................................................................................................................................................ 84
Thermodynamics – I .............................................................................................................................. 84
 Brief Resume of First and Second Law of Thermodynamics .......................................................... 84
 Entropy Changes in Reversible and Irreversible Processes ............................................................. 87
 Variation of Entropy with Temperature, Pressure and Volume ...................................................... 92
 Entropy Concept as a Measure of Unavailable Energy and Criteria for the Spontaneity of Reaction
...........................................................................................................................................................94
 Free Energy, Enthalpy Functions and Their Significance, Criteria for Spontaneity of a Process ... 98
 Partial Molar Quantities (Free Energy, Volume, Heat Concept) ................................................... 104
 Gibb’s-Duhem Equation ................................................................................................................ 108
 Problems ........................................................................................................................................ 111
 Bibliography .................................................................................................................................. 112
CHAPTER 3 .............................................................................................................................................. 113
Chemical Dynamics – I ........................................................................................................................ 113
 Effect of Temperature on Reaction Rates ...................................................................................... 113
 Rate Law for Opposing Reactions of Ist Order and IInd Order..................................................... 119
 Rate Law for Consecutive & Parallel Reactions of Ist Order Reactions ....................................... 127
 Collision Theory of Reaction Rates and Its Limitations ............................................................... 135
 Steric Factor................................................................................................................................... 141
 Activated Complex Theory ........................................................................................................... 143
 Ionic Reactions: Single and Double Sphere Models ..................................................................... 147
 Influence of Solvent and Ionic Strength ........................................................................................ 152
 The Comparison of Collision and Activated Complex Theory ..................................................... 157
 Problems ........................................................................................................................................ 158
 Bibliography .................................................................................................................................. 159
CHAPTER 4 .............................................................................................................................................. 160
Electrochemistry – I: Ion-Ion Interactions ..................................................................................... 160
 The Debye-Huckel Theory of Ion-Ion Interactions ....................................................................... 160
 Potential and Excess Charge Density as a Function of Distance from the Central Ion ................. 168
 Debye-Huckel Reciprocal Length ................................................................................................. 173
 Ionic Cloud and Its Contribution to the Total Potential ................................................................ 176
 Debye-Huckel Limiting Law of Activity Coefficients and Its Limitations ................................... 178
 Ion-Size Effect on Potential ........................................................................................................... 185
 Ion-Size Parameter and the Theoretical Mean - Activity Coefficient in the Case of Ionic Clouds with
Finite-Sized Ions ............................................................................................................................ 187
 Debye-Huckel-Onsager Treatment for Aqueous Solutions and Its Limitations ............................ 190
 Debye-Huckel-Onsager Theory for Non-Aqueous Solutions........................................................ 195
 The Solvent Effect on the Mobility at Infinite Dilution ................................................................ 196
 Equivalent Conductivity (Λ) vs Concentration C1/2 as a Function of the Solvent ......................... 198
 Effect of Ion Association Upon Conductivity (Debye-Huckel-Bjerrum Equation) ...................... 200
 Problems ........................................................................................................................................ 209
 Bibliography .................................................................................................................................. 210
CHAPTER 5 .............................................................................................................................................. 211
Quantum Mechanics – II .................................................................................................................... 211
 Schrodinger Wave Equation for a Particle in a Three Dimensional Box ...................................... 211
 The Concept of Degeneracy Among Energy Levels for a Particle in Three Dimensional Box .... 215
 Schrodinger Wave Equation for a Linear Harmonic Oscillator & Its Solution by Polynomial Method
.........................................................................................................................................................217
 Zero Point Energy of a Particle Possessing Harmonic Motion and Its Consequence ................... 229
 Schrodinger Wave Equation for Three Dimensional Rigid Rotator .............................................. 231
 Energy of Rigid Rotator ................................................................................................................ 241
 Space Quantization ........................................................................................................................ 243
 Schrodinger Wave Equation for Hydrogen Atom: Separation of Variable in Polar Spherical
Coordinates and Its Solution ......................................................................................................... 247
 Principal, Azimuthal and Magnetic Quantum Numbers and the Magnitude of Their Values ....... 268
 Probability Distribution Function .................................................................................................. 276
 Radial Distribution Function ......................................................................................................... 278
 Shape of Atomic Orbitals (s, p & d) .............................................................................................. 281
 Problems ........................................................................................................................................ 287
 Bibliography .................................................................................................................................. 288
CHAPTER 6 .............................................................................................................................................. 289
Thermodynamics – II ........................................................................................................................... 289
 Clausius-Clapeyron Equation ........................................................................................................ 289
 Law of Mass Action and Its Thermodynamic Derivation ............................................................. 293
 Third Law of Thermodynamics (Nernst Heat Theorem, Determination of Absolute Entropy,
Unattainability of Absolute Zero) And Its Limitation ................................................................... 296
 Phase Diagram for Two Completely Miscible Components Systems ........................................... 304
 Eutectic Systems (Calculation of Eutectic Point) .......................................................................... 311
 Systems Forming Solid Compounds AxBy with Congruent and Incongruent Melting Points ....... 321
 Phase Diagram and Thermodynamic Treatment of Solid Solutions.............................................. 332
 Problems ........................................................................................................................................ 342
 Bibliography .................................................................................................................................. 343
CHAPTER 7 .............................................................................................................................................. 344
Chemical Dynamics – II ...................................................................................................................... 344
 Chain Reactions: Hydrogen-Bromine Reaction, Pyrolysis of Acetaldehyde, Decomposition of
Ethane ............................................................................................................................................ 344
 Photochemical Reactions (Hydrogen-Bromine & Hydrogen-Chlorine Reactions) ....................... 352
 General Treatment of Chain Reactions (Ortho-Para Hydrogen Conversion and Hydrogen-Bromine
Reactions) ....................................................................................................................................... 358
 Apparent Activation Energy of Chain Reactions .......................................................................... 362
 Chain Length ................................................................................................................................. 364
 Rice-Herzfeld Mechanism of Organic Molecules Decomposition (Acetaldehyde) ...................... 366
 Branching Chain Reactions and Explosions (H2-O2 Reaction) ..................................................... 368
 Kinetics of (One Intermediate) Enzymatic Reaction: Michaelis-Menten Treatment .................... 371
 Evaluation of Michaelis's Constant for Enzyme-Substrate Binding by Lineweaver-Burk Plot and
Eadie-Hofstee Methods ................................................................................................................. 375
 Competitive and Non-Competitive Inhibition ............................................................................... 378
 Problems ........................................................................................................................................ 388
 Bibliography .................................................................................................................................. 389
CHAPTER 8 .............................................................................................................................................. 390
Electrochemistry – II: Ion Transport in Solutions ....................................................................... 390
 Ionic Movement Under the Influence of an Electric Field ............................................................ 390
 Mobility of Ions ............................................................................................................................. 393
 Ionic Drift Velocity and Its Relation with Current Density .......................................................... 394
 Einstein Relation Between the Absolute Mobility and Diffusion Coefficient .............................. 398
 The Stokes-Einstein Relation ........................................................................................................ 401
 The Nernst-Einstein Equation ....................................................................................................... 403
 Walden’s Rule ............................................................................................................................... 404
 The Rate-Process Approach to Ionic Migration ............................................................................ 406
 The Rate-Process Equation for Equivalent Conductivity .............................................................. 410
 Total Driving Force for Ionic Transport: Nernst-Planck Flux Equation ....................................... 412
 Ionic Drift and Diffusion Potential ................................................................................................ 416
 The Onsager Phenomenological Equations ................................................................................... 418
 The Basic Equation for the Diffusion ............................................................................................ 419
 Planck-Henderson Equation for the Diffusion Potential ............................................................... 422
 Problems ........................................................................................................................................ 425
 Bibliography .................................................................................................................................. 426
INDEX ......................................................................................................................................................... 427

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CHAPTER 5

Figure 1. The particle in a three-dimensional box.

Copyright © Mandeep Dalal

After putting the value of three-dimensional Hamiltonian in equation (1), we get

Since E is negligible in comparison to the ∞, the above equation becomes

𝜕2𝜓 𝜕2𝜓 𝜕2𝜓 (7)

𝜕2𝜓 𝜕2𝜓 𝜕2𝜓 (8)

1 𝜕2𝜓 𝜕2𝜓 𝜕2𝜓 (9)

𝜓(𝑥, 𝑦, 𝑧) = 𝜓(𝑥) × 𝜓(𝑦) × 𝜓(𝑧) = 𝑋𝑌𝑍 (12)

Using the above expression in equation (11), we get

𝜕 2 𝑋𝑌𝑍 𝜕 2 𝑋𝑌𝑍 𝜕 2 𝑋𝑌𝑍 8𝜋 2 𝑚𝐸 (13)

𝜕2𝑋 𝜕2𝑌 𝜕 2 𝑍 8𝜋 2 𝑚𝐸 (14)

Now divide the above equation by XYZ on both side i.e.

1 𝜕2𝑋 1 𝜕2𝑌 1 𝜕2𝑍 (17)

1 𝜕2𝑋 1 𝜕2𝑌 1 𝜕2𝑍 (18)

Similarly, the solution of equation (20) will be

𝑛𝑥2 𝑛𝑦2 𝑛𝑧2 ℎ2 (26)

 The Concept of Degeneracy Among Energy Levels for a Particle in Three

𝑛𝑥2 𝑛𝑦2 𝑛𝑧2 ℎ2 (28)

Similarly, the energy expression also changes to

If 𝑛𝑥 = 𝑛𝑧 = 1 and 𝑛𝑦 = 2; the wavefunction and energy become

Copyright © Mandeep Dalal

If 𝑛𝑦 = 𝑛𝑧 = 1 and 𝑛𝑥 = 2, the state with energy becomes

 Schrodinger Wave Equation for a Linear Harmonic Oscillator & Its

Figure 2. The pictorial representation of the displacement-inducing in a typical spiral.

Copyright © Mandeep Dalal

The total work from zero displacement to ‘x’ displacement will be

Figure 3. The variation of potential energy as a function of displacement in a classical oscillator.

𝜕2𝜓 8𝜋 2 𝑚𝐸 16𝜋 4 𝑚2 𝜈 2 𝑥 2 (49)

After defining constants

Now define a new variable 𝑦 = √𝛽𝑥, then we have the derivative as

Dividing the above equation by β, we get

The two possible solutions of the above equation are

Differentiating again, we get

Differentiating the above equation, we get

Differentiating again, we get

Using equation (68-70) in equation (67), we get

[2𝑎2 + 6𝑎3 𝑦 + 12𝑎4 𝑦 2 … ] − 2𝑦[𝑎1 + 2𝑎2 𝑦 + 3𝑎3 𝑦 2 + 4𝑎4 𝑦 3 … ] (71)

[2𝑎2 + 6𝑎3 𝑦 + 12𝑎4 𝑦 2 … ] − [2𝑎1 𝑦 + 4𝑎2 𝑦 2 + 6𝑎3 𝑦 3 + 8𝑎4 𝑦 4 … ] (72)

After further rearranging

For n = 1, the equation (82) becomes

𝐻1 (𝑦) = (−1). (−2𝑦). 𝑒 𝑦

For n = 2, the equation (82) becomes

𝐻2 (𝑦) = (4𝑦 2 − 2)𝑒 𝑦

α/β n Hn(y) ψn(y) ψn(x)

7 3 8𝑦 3 − 12𝑦 𝑁3 (8𝑦 3 − 12𝑦)𝑒 −𝑦

Furthermore, we also know that

 Zero Point Energy of a Particle Possessing Harmonic Motion and Its

Also, the general expression for the energies is given below.

Copyright © Mandeep Dalal

 Schrodinger Wave Equation for Three Dimensional Rigid Rotator

Copyright © Mandeep Dalal

Now since 𝑟 = 𝑟1 + 𝑟2 , we rearrange equation (124) to give

In the two-mass system 𝐼 = 𝑚1 𝑟12 + 𝑚2 𝑟22 , so have

The expression for the operator 𝐿̂2 in polar coordinates is

𝜓(𝜃, 𝜙) = 𝜓(𝜃) × 𝜓(𝜙) = 𝛩 × 𝛷 (141)

After putting the value of equation (141) in equation (140), we get

1 𝜕 𝜕𝛩𝛷 1 𝜕𝛩𝛷 8𝜋 2 𝐼𝐸𝛩𝛷 (142)

After multiplying equation (144) by 𝑆𝑖𝑛2 𝜃, we get

At this point, we can set both sides equal to constant m2 i.e.