CHM 112M: Lecture 5

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Arnab Ghosh
August 24, 2023

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1 Hydrogen Atom
For a hydrogenic system1 , PE due to Coulomb interaction between negatively
charged electron and positively charged nucleus +Ze is given by

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p
V (x, y, z) = −Ze2 / (x2 + y 2 + z 2 ), (1)
p
which only depends on the radial distance r = (x2 + y 2 + z 2 ) between the
nucleus and electron and can be identified as V (r) = −Ze2 /r. Such potential
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is called central potential and the corresponding TISE is
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h̄2
 2
∂2 ∂2 Ze2

∂
− + 2+ 2 −p ψ(x, y, z) = Eψ(x, y, z). (2)
2µ ∂x2 ∂y ∂z (x2 + y 2 + z 2 )
Mathematically, such problems are hard to solve in Cartesian coordinates and
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are most conveniently handled in spherical polar coordinates, since the poten-
tial V (r) has a spherical symmetry about the nucleus and thus the problem is
classified as a central field problem. By a proper transformation, Eq (2) which
is expressed in Cartesian coordinates, can be converted into spherical polar
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coordinates (Try), as follows:

h̄2 1 ∂ 1 1 ∂2
       
2 ∂ 1 1 ∂ ∂
− r + sin θ + + V (r) ψ(r, θ, φ)
2µ r2 ∂r ∂r r2 sin θ ∂θ ∂θ r2 sin2 θ ∂φ2
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= Eψ(r, θ, φ) (3)
Following the separation of variables procedure for the wave function
ψ(r, θ, φ) = R(r)Θ(θ)Φ(φ) (4)
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in Eq. (2) and dividing the result by R(r)Θ(θ)Φ(φ), we get after rearrangement
   
1 d 2 dR(r) 1 1 d dΘ(θ)
r + sin θ
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r2 R(r) dr dr r2 sin θΘ(θ) dθ dθ

2
1 1 d Φ(φ) 2µ(E − V (r))
+ 2 + =0 (5)
r sin2 θΦ(φ) dφ2 h̄2
| {z }
×r 2 sin2 θ
1 Note: This is Brief Overview of Class Topics (For Internal Use): Not a Lecture Substitute.

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 Upon multiplication by r2 sin2 θ, we find that in the resulting equation the term
(1/Φ)d2 Φ/dφ2 depends only on φ. Denoting the constant by −m2 , following
the previous procedure, we can write

1 d2 Φ(φ)

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= −m2 . (6)
Φ(φ) dφ2

Further, being multiplied by r2 , Eq. (5), can be written as

   
1 d 2 dR(r) 1 d dΘ(θ)
r + sin θ
R(r) dr dr Θ(θ) sin θ dθ dθ

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| {z } | {z }
depends on r depends on θ

1 d2 Φ(φ) 2µr2 (E − V (r))

+ + =0 (7)
sin2 θΦ(φ) dφ2 h̄2
} | {z }

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| {z
depends on θ depends on r

Following the same logic, collecting the θ and r-dependent terms and equating
them to a constant, say −β, we write

1 d

G dΘ(θ)

m2
sin θ − = −β (8)
Θ(θ) sin θ dθ dθ sin2 θ

and rearranging terms, we get

   
1 d dR(r) β 2µ(E − V (r))
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r2 + − 2+ R(r) = 0 (9)
r2 dr dr r h̄2

Now, we have to solve above three boxed equations.

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1.1 Solution of the φ-dependent part

The solution of the 2nd order differential Eq. (6) is of the form Aeimφ , where m
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is the magnetic quantum number. To ensure that the function is single valued, it
is essential Φ(φ0 ) = Φ(φ0 ±2mπ). This condition is satisfied if m = 0, ±1, ±2, ....
R 2π √
Normalization condition 0 Φ∗ (φ)Φ(φ)dφ = 1, yields A = 1/ 2π. Therefore,
the normalized wave function is
R

1
Φ(φ) = √ eimφ . (10)
2π

1.2 Solution of the θ-dependent part

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Eq. (8) is much difficult to solve. Introducing new independent variable z =

cos θ, one can rewrite (Try) in terms of P (z) = Θ(θ)

m2
   
d 2 dP (z)
(1 − z ) + β− P (z) = 0, (11)
dz dz 1 − z2

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 Note, the range of 0 ≤ θ ≤ π changes to −1 ≤ z ≤ 1, and as a result the above
differential equation has singularities at z = ±1. In order to include z = ±1
and hence to make P (z) = Θ(θ) an acceptable wave function, β is restricted to
take values only

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β = l(l + 1), l = 0, 1, 2, 3, .... (12)

where l is called the azimuthal quantum number. Now, for a given value of l, the
|m|
acceptable wave function is given by the associated Legendre function, Pl (z),
|m|
via Θlm (θ) = APl (z), where m = 0, ±1, ±2, ±3, ... ± l. The normalization
|m| |m|
constant is obtained by A2 Pl Pl dz = 1 and the normalized wave function
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is given by
p
(2l + 1)(l − |m|)! |m|
Θlm (θ) = p Pl (z), (13)
2(l + |m|)!

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where associated Legendre function

|m| d|m| Pl (z)

Pl (z) = (1 − z 2 )|m|/2 , (z = cos θ) (14)
G dz |m|
is obtained by differentiating Legendre polynomial Pl (z). With P0 (z) = 1 and
P1 (z) = z = cos θ (Try P2 ), Pl (z) can be evaluated for any value of l by using
the recursion relation

(l + 1)Pl+1 (z) − (2l + 1)zPl (z) + lPl−1 (z) = 0.

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(15)

Find out: Θ00 (θ), Θ10 (θ), Θ11 (θ), Θ20 (θ), Θ21 (θ), Θ22 (θ), Θ30 (θ).
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1.3 The solution of the r-dependent part

For hydrogenic systems, the PE, V (r) = −Ze2 /r, where Z is the atomic number
of the atom or ion. Further, substituting the value of β from Eq. (12) into
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Eq. (9), we get

   
1 d 2 dR(r) l(l + 1) 2µ(E − V (r))
r + − + R(r) = 0 (16)
r2 dr dr r2 h̄2
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The process of solving, yields the expressions for the quantized energy levels of
the hydrogenic systems as

2π 2 µZ 2 e4
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En = − , n = 1, 2, 3, ... (17)
n2 h2
where n = nr +l +1 with nr as the radial quantum number. Since, l and nr both
can take values 0, 1, 2, 3, ...., therefore principle quantum number n has values
1, 2, 3..... Note, above equation is identical to the energy level expression pro-
vided by Bohr for stationary states, except that me is Bohr’s theory is replaced

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 here by the reduced mass µ. Finally, the solution of the radial part of the wave
function turns out to be

Rnl (r) = Nnl ρl Lnl (ρ)e−ρ/2 , (18)

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where for convenience we define ρ = 2Zr/na0 , a0 = 4πh2 µe2 is the Bohr radius,
and Ln,l (ρ) is the associated Laguerre polynomial and Nnl is the normalization
constant. Now, we have the full solution of the TISE Eq. (2) as

ψnlm (r, θ, φ) = Rnl (r)Θlm (θ)Φm (φ) ≡ Rnl (r)Ylm (θ, φ),

where the product function Θlm (θ)Φm (φ), often represented to as Ylm (θ, φ), and

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known as spherical harmonics. The process of deriving the solutions yield three
quantum numbers with the following relationship between them:

n = 1, 2, 3...., l = 0, 1, 2, 3, ...n − 1, m = 0, ±1, ±2, ... ± l, (19)

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where the nomenclature for various l states are of spectroscopic origin 2 . For
each n we have n number of l values and for each l we have 2l + 1 number of m
values. Thus the degree of degeneracy for an energy level can be computed as
G
n−1
X
gn = 2l + 1 = n2 (20)
n=0

An one electron wave function ψnlm described by the combinations of Rnl (r)
and Ylm (θ, φ) is called an orbital. It is apparent from Eqs. (6) and (8) that
the angular part of the wave function is an eigenfunction of the L̂2 operator,
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satisfying the following equation:

1 ∂2
   
2 2 1 ∂ ∂
L̂ Y (θ, φ) ≡ −h̄ sin θ + Θ(θ)Φ(φ) = L2 Y (θ, φ) (21)
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sin θ ∂θ ∂θ sin2 θ ∂φ2

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with an eigenvalue L√ = l(l + 1)h̄2 . Since Y (θ, φ) is a product two functions
Θ(θ) and Φ(φ) = (1/ 2π)eimφ , it can be written as
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Y (θ, φ) = Θ(θ)Φ(φ) ≡ f (θ)eimφ , (22)

where m takes any positive or negative integers, including zero. This imme-
diately follows that the above wave functions are also eigenfunctions of the
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z-component of the angular momentum operator with eigenvalue mh̄:

∂
f (θ)eimφ = −ih̄f (θ).imeimφ = mh̄Y (θ, φ).


L̂z Y (θ, φ) = −ih̄ (23)
∂φ
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Hence, spherical harmonics are eigenfunctions of both L̂2 and L̂z operators:

L̂2 Ylm (θ, φ) = l(l + 1)h̄2 Ylm (θ, φ)

L̂z Ylm (θ, φ) = mh̄Ylm (θ, φ), m = 0, ±1, ±2, ... ± l (24)
2l = 0, 1, 2, 3, .. correspond to s (sharp), p (principle), d (diffuse), and f (fundamental)..

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 z
|L| = l(l + 1)ℏ

Lz = mℏ

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x, y

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Figure 1: Vector model of the angular momentum in an atom.

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This implies that we can’t specify the exact direction of L, i.e., all components
of L can’t be known simultaneously , only |L|2 and Lz can be specified simulta-
neously. One should note there is nothing special in z-direction, it is just one of
the three orthogonal directions. This simply means that two orthogonal com-
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ponents of angular momentum may not be known simultaneously which indeed
follows from the angular momentum commutation relations. For this reason,
pictorially, quantum mechanical angularp momentum states are represented by
a vector model, with a vector of length l(l + 1)h̄, angled in such a way that
its component along z-axis is equal to mh̄ and its tip moving in a circular ring
[Fig. 1]. Sometimes, it is convenient to use linear combinations of the angular
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part Ylm (θ, φ) to produce trigonometric representations useful for visualization.

For example, l = 1, the m takes values m = 0, ±1 and the last two are combined
to give the real 2px and 2py orbitals. This follows from the following functional
dependencies from Eq. (22):
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p+1 ∼ sin θeiφ ; p0 ∼ cos θ; p−1 ∼ sin θe−iφ

Then we identify pz = p0 ∼ cos θ ∼ z and

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p+1 + p−1 p+1 − p−1

px = √ ∼ sin θ cos φ ∼ x; py = −i √ ∼ sin θ sin φ ∼ y. (25)
2 2
Construct dz2 , dxz , dyz , dx2 −y2 , dxy orbitals from the following relations:
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d+2 ∼ sin 2 θ2iφ ; d+1 ∼ sin θ cos θeiφ ; d0 ∼ 3 cos 2 θ − 1; d−1 sin θ cos θe−iφ ; d−2 ∼ sin 2 θ−2iφ

Reference:
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1. Atomic Electronic Structure by P. K. Ghosh and P. K. Shukla. (PKG)