Chapter four

Introduction to Quantum Mechanics

4.1 Schrödinger wave equation

 Imagine a particle of mass m, constrained to move along x- axis, subject to some

specified force F(x,t) (figure 4.1).
 Classical mechanics: determine the position of the particle at any given time: x(t).,
by applying newtons second law: F=ma with appropriate initial conditions.

Figure 4.1: A “particle” constrained to move in one dimension under the influence of a specified
force.
 Quantum mechanics: approaches the same problem quite differently. In this case
what we’re looking for is the wave function, Ψ(x,t), of the particle, and we get it by
solving the Schrodinger equation:

𝜕Ψ ħ2 𝜕2 Ψ
𝑖ħ = − + 𝑉Ψ (4.1)
𝜕𝑡 2𝑚 𝜕𝑥 2

 The Schrödinger equation plays a role logically analogous to newton’s second law:
Given suitable initial conditions [typically Ψ(x,0) ], the Schrödinger equation
determines Ψ(x,t) for all future time, just as, in classical mechanics, Newton’s law
determines x(t) for all future time.

4.1.1 Normalization and Probability

 As discussed in chapter 3, the wave function found from Schrödinger equation

describes the state of the particle.
But how the wave function (which spread out in space) can describe the state of the
particle?

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 The answer is provided by Born’s statistical interpretation of the wave function, which
2
says that gives the probability of finding the particle at point x, at time t
or more precisely,

𝛹 𝑥 𝑡 (4.2)

Figure 4.2 A typical wave function. The particle would be relatively likely to be found
near A, and unlikely to be found near B. The shaded area represents the probability of
finding the particle in range dx.
 Wave functions are usually complex with real and imaginary parts. The probability
2
density for complex is therefore taken as the product of of and its
complex conjugate . Indeed it is real quantity.

2
 We have identified is proportional to the probability density P of finding the
2
body at point x, at time t described by , the integral of over all space
must be finite-the body is somewhere, after all, If

2
∫ = (4.3)
A wave function that obeys 4.3 is said to be normalized. Every acceptable wave
function can be normalized by multiplying it by an appropriate constant.

4.1.2 Expectation Value

 Once the wave function for a particle is known, it is possible to calculate the average
position at which you would expect to find the particle after many measurements.
 This average position is called the expectation value of x and is defined by the
equation.
〈 〉=∫ 4.4
 Brackets, 〈 〉 , are used to denote expectation values.) Furthermore, one can find the
expectation value of any function f(x) associated with the particle by using the
following equation

〈 〉 ∫ 4.5

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 4.1.3 Boundary conditions
 In quantum mechanics, it is very common for particles to be subject to boundary
conditions.
 For example: 1. Because the ends of the string must be nodes, the wave functions for
allowed waves must be zero at the boundaries of the string.
2. Because the particle in a box cannot exist outside the box, the allowed
wave functions for the particle must be zero at the boundaries.
 The boundary conditions on the string waves lead to quantized wavelengths and
frequencies of the waves.
 The boundary conditions on the wave function for the particle in a box lead to
quantized wavelengths and frequencies of the particle.

Example 4.1 At time t=0 a particle is represented by the wave function

Ax/a, if 0
= A(b - x)/(b - a) if a
0, otherwise,
Where A, a and b are constants.
a. Normalize (that is find A in terms of a and b).
b. Sketch as a function of x.
c. Where is the particle most likely to be found, at t=0?
d. What is the probability of finding the particle to the left of a?

4.2 Time independent Schrödinger equation

 In previous sections we have seen how you use a wave function to calculate various
quantities of interest.
 Now we are going to see how Ψ(x,t) found from Schrödinger equation.
 Assume first the potential V, is independent of t (time). In that case the Schrödinger
equation can be solved by the method of separation of variables: We look for
solutions that are simple products
Ψ(x,t)= (x) f(t) 4.6
 Where ψ (lowercase) is the function of x alone and f is a function of t alone.
For separable solutions we have
2 2
= , 2
= 2
 Substituting these results in Schrödinger equation we have
ħ2 2
ħ = − 2
+
2

 Or dividing through by
ħ
ħ = − +V 4.7

 Now the left side is a function of t alone, and the right side is a function of x alone.
The only way this equation satisfied is if both sides equal to a constant.

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 Let’s call the separation constant E, then
ħ = = − ħ
4.8

ħ2 2
And − 2
+ = multiplying both side by psi( ) we get
2

ħ𝟐 𝒅𝟐 𝛙
− + 𝑽𝛙 = 𝐄𝛙
𝟐𝒎 𝒅𝒙𝟐 4.9

 Equation 4.8 is easy to solve , the general solution is C exp(-iEt/ħ but we might absorb
the constant C into
ħ
f(t) = 4.10
 The equation 4.9 is called the time independent Schrödinger equation; we can go no
further with it until the potential; V(x) is specified.
 The rest of this chapter will be devoted to solving the time independent Schrödinger
equation .

4.3 Square well potential

4.3.1 Infinite square well
 Suppose
V(x) = 0, if 0
4.11

 A particle in this potential is completely free, except at the two ends (x=0 and x=a),
where an infinite force prevents it from escaping (figure 4.3).
 A classical model would be a cart on frictionless horizontal air track, with perfectly
elastic bumpers-it just keeps bouncing back and forth forever.

Figure 4.3 The infinite square well potential.

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  Outside the well, (x)=0 (the probability of finding the particle there is zero). Inside the
well, where V=0, the time independent Schrödinger equation reads
ħ2 2
− 2 = 4.12
2
Or
2
√2
= − 22 4.13
ħ
 The general solution is for 4.13
(x) = + 4.14
where A and B are arbitrary constants. Typically these constants are fixed by the
boundary conditions of the problem.
 Always for the wave function and its first derivative ( ) are continuous.
 Continuity of (x) requires that
(0)= (a) = 0,
 Then from eq 4.14 putting x=0

(0) = + =
So B=0, and hence
(x) = 4.15

 Then (a) = so either A=0 [in which case we are left with the trivial non-
normalizable solution (x)=0], or else = which means that
= 4.16
 And since sin (- ) = -sin ( ) so we can absorb the minus sign into A, no need of negative
solutions! Therefore the distinct solutions are
= With n=1, 2, 3, …. 4.17
 Hence the possible values of E:
ħ2 2 2 2 ħ2
= = 2 4.18
2 2
 Because the lowest energy of the particle in a box is not zero, then, according to quantum
mechanics, the particle can never be at rest! The smallest energy it can have,
corresponding to n = 1, is called the ground-state energy.
 Now we fix the constant A by normalizing
2 2 2 2
∫ = = =
 Inside the well, then the solutions are

2
(x)=√ 4.19

 The total wave function will be then (eq 4.6)

2 ħ
Ψ(x,t)= (x) f(t) = √ 4.20

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 Which is called a stationary solution since the probability density does not depend on
time.

Figure 4.4 The first stationary states of the infinite square well

Example: An electron is confined between two impenetrable walls 0.200nm apart. a)

Determine the energy levels for the states n= 1, 2, and 3. B) Find the speed of the
electron in the n = 1 state.
Ans Hint: First calculate E1 by eq 4.18 so E1 =1.51 x 10-18 J = 9.42 eV En=n2E1
The speed u=1.82 x 106 m/s

Example: A particle of mass m is confined to a one-dimensional box between x = 0 and

x = a. Find the expectation value of the position x of the particle in the state
characterized by quantum number n.
Ans a/2

4.3.2 Finite well Potential

 Now consider a particle in a finite potential well, that is, a system having a potential
energy that is zero when the particle is in the region 0 < x < L and a finite value U
when the particle is outside this region as in Figure 4.4.
 Classically, if the total energy E of the system is less than U, the particle is permanently
bound in the potential well.
 If the particle were outside the well, its kinetic energy would have to be negative, which
is impossibility.
 According to quantum mechanics, however, a finite probability exists that the particle
can be found outside the well even if E < U. That is, the wave function c is generally

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 nonzero outside the well—regions I and III in Figure 4.4—so the probability density
2
is also nonzero in these regions.

Figure 4.4 Potential-energy diagram of a well of finite height U and length 2a .

 In region II, where U = 0, the allowed wave functions are again sinusoidal because they
represent solutions of Equation 4.13.
 The boundary conditions, however, no longer require that be zero at the ends of the
well, as was the case with the infinite square well.

1) Region I and III

 In these two regions
U(x)=U

 The Schrödinger equation for regions I and III may be written:

2 2
2
= 4.21
ħ2
 Because U > E, the coefficient of on the right-hand side is necessarily positive.
 Therefore, we can express Equation 4.21 as
2
2
2
= 4.22
√ − ⁄ħ is a positive constant in regions I and III
 As you can verify by substitution, the general solution of Equation 4.22 is
= + − 4.23
 If the particle is in region I, the x is always negative. If x − the term
and . Since this cannot be true, that means B=0.
 Therefore = if particle is in region I.
 If the particle is in region III, by similar argument, A=0.
 Therefore, = − if the particle is in region III.

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 2) Region II
 In this region
U(x)= 0
 The schrodinger equation is
2
2 √
2
= −
ħ
Then the wave function is: (x) = +

 Now we could have two solution one even (symmetric) the other odd(anti symmetric).
 Let’s stick on the even solution

 In this case − = therefore

i) = Which implies A=B
ii) Should be even which demand F=0 (no sin(kx) )
 The wave functions become then
= , (x) = , (x)= − 4.25

Applying the boundary conditions

 For the wave functions to be physically measurable it must be continuous throughout, even
at x=-a and x=a. Also the slope at these two points(derivatives) must exist.

𝑑ψ 𝑑ψ2
ψ = ψ2 = 𝑖𝑓 𝑥 = −𝑎
𝑑𝑥 𝑑𝑥

𝑑ψ2 𝑑ψ
ψ2 = ψ = 𝑖𝑓 𝑥 = 𝑎
𝑑𝑥 𝑑𝑥

If we set x=a; 2 = ⇒
= − (*)
2
And setting = ⇒
− = -A − (**)
aking the ratio of ** to * we get
= 4.26

 The transcendental equation (4.26) cannot be solved directly; we can solve them
either graphically or numerically to get energy expression for the infinite well:

2 ħ2
2
= 2
4.27

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Quantum Tunneling
 From our discussion of particle in a finite potential well we saw that in quantum
mechanics, a particle can penetrate a potential barrier and enter a region that is
normally forbidden by classical mechanics.


 A ball of mass m is on the ground (U=0) and is moving with a kinetic energy, KE,
when it begins ascending a hill of height h. If the potential of hill is too high, the ball
will never make to the other side (KE< U= mgh).
 Suppose now we have a particle of mass m and no potential energy (U=0) moving
with kinetic energy E0=KE when it encounters a potential barrier such that KE < V!
According to classical mechanics, particle should simply bounce off and travels in
reverse.
 According to quantum mechanics, there is a non-zero probability that the particle will
end up on the other side, even though KE < U!
 A free particle has a form of a sinusoidal wave. When the wave enters the potential
region, the wave function begins to decrease exponentially. But before it decreases to
zero, it resurfaces and continues to move, although with a smaller amplitude.

 The ability of the particle to penetrate barriers is known as quantum tunneling.

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  Transmission coefficient (T)- fraction of particles that make it across
 Reflection coefficient (R)- fraction of particle that reflect

2 √2
T + R =1 T where = 4.28
ħ

4.4 Simple Harmonic Oscillator

 Consider a particle that is subject to a linear restoring force F = -kx, where k is a

constant and x is the position of the particle relative to equilibrium (x = 0).
 The potential energy of the system is given by,
U= k 2 = 2 2
4.29
2 2

where the angular frequency of vibration is =√ ⁄

 Such problem is used for understanding problems such as vibrations of a mass on a
spring, vibrations of atoms in a solid.
 In quantum mechanics also, the harmonic oscillator problem is quite important.

Classically,
 If the particle is displaced from its equilibrium position and released, it oscillates between
the points x = -A and x = A, where A is the amplitude of the motion.
 Furthermore, its total energy E is,
E = KE + U = k 2 = 2 2
4.30
2 2
 In the classical model, any value of E is allowed, including E = 0, which is the total
energy when the particle is at rest at x = 0.
Quantum Mechanically,
2 2
 The Schrödinger equation for this problem is obtained by substituting U= into
2
eq (4.9)
ħ2 2
2 2
− 2
+ = 4.31
2 2
which can be reduced to
2 2 2
2
+ − ) =0 4.32
ħ2 2

= √ħ⁄ is a constant that has dimensions of length;

 This equation can be recast so that it becomes a well-known differential equation with
solutions known as Hermite polynomials
 or we can guess the solution
2
= 4.33
Substituting this function into Eq 4.31 shows that it is a satisfactory solution to the
Schrödinger equation, provided that
C= and E = ħ
2ħ 2

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  It turns out that the solution we have guessed corresponds to the ground state of the
system, which has an energy ħ .
2
 Because = , t follows from Equation (4.33) that the wave function for this state is
2ħ
( ) 2
= ħ 4.34
where B is a constant to be determined from the normalization condition.
 This result is but one solution to Equation 4.31. The remaining solutions that describe the
excited states are more complicated!
 The energy levels of a harmonic oscillator are quantized as we would expect because the
oscillating particle is bound to stay near x = 0. The energy of a state having an arbitrary
quantum number n is
= + ⁄ ħ where n= 0, 1, 2, 3

Figure 4.5 Energy-level diagrams for a simple harmonic oscillator, superimposed on the potential
energy function.
 In a classical harmonic oscillator, the energy of the oscillator is continuous and can be
increased by increasing the amplitude of vibration. In the quantum treatment, the energy
increases in steps of ħ .

Band Theory of Solids

 Quantum mechanics in general and quantum statistics in particular have had spectacular
success in explaining properties of solid-state materials.
 Why some materials are metals and have very high conductivity, while others are
insulators with low conductivity?
 Note that both metals and insulators have a very high density of electrons (about 1022
cm3).
 The answer to the question lies in Fermi statistics and in the band theory of solids.

 The distance between adjacent copper atoms in solid copper is 260 pm.

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  Each of these isolated neutral atoms stacks up its 29 electrons in an array of discrete
subshells as follows:

1s2 2s2 2p6 3s2 3p6 3d10 4s1.

 Recall, for example, that the subshell with principal quantum number n = 3 and orbital
quantum number l=1 is called the 3p subshell; it can hold up to 2(2l + 1) = 6 electrons.
 We see above that the first six subshells in copper are filled, but the (outermost) 4s
subshell, which can hold two electrons, holds only one.
 If we bring the atoms of copper closer together, their wave functions will start to
overlap, beginning with those of the outermost electrons.
 When the wave functions of the two atoms overlap, we speak not of two independent
atoms but of a single two atom system; here the system contains 2 x 29 = 58 electrons.
 The Pauli Exclusion Principle also applies to this larger system and requires that each
of these 58 electrons occupy a different quantum state. In fact, 58 quantum states are
available because each energy level of the isolated atom splits into two levels for the
two-atom system.
 If we bring up more atoms, we gradually assemble a lattice of solid copper.
 If our lattice contains, say, N atoms, then each level of an isolated copper atom must
split into N levels in the solid.
 Thus, the individual energy levels of the solid form energy bands, adjacent bands
being separated by an energy gap, with the gap representing a range of energies that
no electron can possess.
 A typical band ranges over only a few electron volts.

Figure ) Theband–gap pattern of energy levels for an idealized crystalline solid. As the magnified view
suggests, each band consists of a very large number of very closely spaced energy levels. (In many solids,
adjacent bands may overlap; for clarity, we have not shown this condition.)

 An important parameter in the band theory is the Fermi level, the top of the available electron
energy levels at low temperatures. The position of the Fermi level with the relation to the
conduction band is a crucial factor in determining electrical properties.
 When an allowed band is completely filled with electrons, the electrons in the band cannot
conduct any current.


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 Most solid substances are insulators, and in terms of the band theory of solids this implies
that there is a large forbidden gap between the energies of the valence electrons and the
energy at which the electrons can move freely through the material (the conduction
band).
 For intrinsic semiconductors like silicon and germanium, the Fermi level is essentially
halfway between the valence and conduction bands. Although no conduction occurs at 0
K, at higher temperatures a finite number of electrons can reach the conduction band and
provide some current. In doped semiconductors, extra energy levels are added.
 In terms of the band theory of solids, metals are unique as good conductors of electricity.
This can be seen to be a result of their valence electrons being essentially free. In the
band theory, this is depicted as an overlap of the valence band and the conduction band
so that at least a fraction of the valence electrons can move through the material.

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