Schrödinger equation

• Erwin Schrödinger proposed an equation for finding the wavefunction of any system.

• The time-independent Schrödinger equation (TISE) for finding a particle of mass, m, energy, E and moving
in one dimension is

ħ2 ψ
- + 𝑉 𝑥 ψ = 𝐸ψ TISE

where V(x) is the potential energy of the particle at the point, x and E is the total energy. The first term is
related to the kinetic energy where, ħ = h/2π.

• Schrödinger equation is a quantum-mechanical postulate i.e., a logical assumption.

• TISE is justified as we can derive de-Broglie relation from it. = -asinax

ħ2 ψ = acosax
- + 𝑉 𝑥 ψ = 𝐸ψ
Harmonic wave function at t= 0 is Acos (2π/λ)x
ψ
= (𝑉 − E)ψ
ħ2
( ) /
One solution of this equation is ψ = coskx ; k =
ħ2

Cos kx is a wave of wavelength λ = 2π/k as the standard form of a harmonic wave is cos(2πx/λ)

/ ħ2
E-V is the kinetic energy of the particle, Ek; hence k = , so Ek = 2m
ħ2

From classical mechanics, Ek = 2m; so p = 2π  p = which is the de-Broglie relation.

λ
 Born interpretation of the wavefunction

• Wavefunction contains all the dynamic information about the

system it describes.

• Just like the amplitude of an EM wave in a region is interpreted

as its intensity, Maxx Born interpreted the square of the
wavefunction |ψ|2 (= ψ*ψ, if ψ is complex) as the probability
density and ψ is called probability amplitude.

• Probability of finding a particle in the region between, x and x+dx

is proportional to |ψ|2dx (Another postulate)

• As there is always probability of finding given particle in the given

limits ∫ |ψ|2dx = 1.
For a particle free to move in three dimensions, with wavefunction ψ, the
probability of finding a particle at point r with coordinates x,y,z is |ψ|2dτ,
where dτ = dxdydz

• |ψ|2 is always positive and real even if ψ is negative or

complex.

• Both negative and positive regions of a wavefunction

may correspond to a high probability of finding a
particle in a region.
• For example, let us consider a wavefunction, ψ = sin

According to Born interpretation, the probability of finding the particle in a box of length a, is
∫ ψ2𝑑𝑥 = ∫ 𝑠𝑖𝑛2 𝑑𝑥 =

But the probability of finding the particle within the given box should be 1. So we multiply the wavefunction
with a constant called Normalization constant, N, so that probability of finding particle is 1.
 Normalization of the wavefunction

• If ψ is a solution of the Schrödinger equation, then, Nψ is also a solution, where N is any constant.

• This gives freedom to vary the wavefunction by N, hence we can determine the normalization constant, N.

• For a normalized wave function, Nψ, the probability of finding the particle in a given region dx is given by

N2∫ ψ∗ψdx = 1. (not just -∞ to +∞, but within the given limits)

• Wave functions for which the above integral exists are called “square integrals”.

Hence the normalization constant, N is given by

N= /
(∫ ψ∗ψdx)
• In general, the wave functions are normalized to 1.

• For particle moving in 1-D ∫ ψ∗ψdx = 1

• For particle moving in 3-D ∫ ∫ ∫ ψ∗ψd𝑥𝑑𝑦𝑑𝑧 = 1 or ∫ ψ∗ψdτ = 1

• For systems with spherical symmetry,∫ ∫ ∫ ψ∗ψ r2drsinθdθdФ

Where r, is the radius; θ is the colatitude; and Ф is the azimuth.

 Acceptable form of wavefunctions
ħ2 ψ
• Wavefunction must be - + 𝑉 𝑥 ψ = 𝐸ψ

• Square integrable, i.e., not infinite over a finite region. (If not the normalization constant becomes zero.)

• Single-valued (If not, it gives absurdity that there is more than one probability to find a particle at a point.)

• Continuous

• Continuous slope (Schrödinger equation needs a second derivative of a function and if a function is not
continuous second derivative is not possible)
Unacceptable wavefunctions

Not continuous No continuous slope

Not single-valued Infinite at a finite region

Square integrable, Single-valued, Continuous, Continuous slope

1. Cosx in limits (0, ∞) 3. e-x in limits (0, ∞)

• ∫ 𝑒 = −𝑒 /2 + 𝑐
• ∫ 𝐶𝑜𝑠2𝑥 = + +𝑐

Not an acceptable wavefunction • Acceptable wavefunction

• Not square integrable.

4. tanθ in limits (0, ∞)
2. ex in limits (−∞, ∞)
• Not an acceptable wavefunction
• ∫ 𝑒2𝑥 = 𝑒2𝑥/2 + 𝑐
• Discontinuous
• Not an acceptable wavefunction

• Not square integrable.

 Orthogonal and orthonormal functions

Two functions ψi and ψj are orthogonal if

• Sets of functions that are normalized and mutually orthogonal are called orthonormal.

• One trivial consequence of operators following hermiticity and functions being

orthogonal/orthonormal is that it reduces the number of integrals we need to evaluate.
 Common mathematical terms in QC
Operators: Hamiltonian, momentum..,

Eigen functions, Eigen values

Properties of Operators: Hermitian, Commuting/non-commuting

Orthogonal and orthonormal wavefunctions

Expectation value
 Operators
Operator is an expression that carries out a mathematical operation on the wave function ψ.

The operator used in TISE is called Hamiltonian operator named after 19th Century mathematician, William
Hamilton.

Hamiltonian operator

If a equation can be written as (Operator)(function) = (constant factor)*(function), then it is called eigen value
equation

In general, (Operator)(eigenfunction) = (eigenvalue)*(eigenfunction)

Ω is the eigen operator, ψ is the eigen function and ω is the eigen value
For the operators 𝑎𝑛𝑑 ,

which of the following functions are eigenfunctions and if they are what are the eigenvalues?

a) eax b) exp(ax2) c) cos(ax) d) sin(ax)

 (Energy operator)ψ = (Energy value) ψ

If wavefunction ψ and the operator corresponding to the observable Ω of interest are known,
and the wavefunction is an eigenfunction of the operator, then we can predict the outcome of an observation
of the property Ω (in this case energy from the eigenvalue ω.

Some of the common operators are

For the operator form is:

Momentum operator

The kinetic energy operator (From Ek = p2/2m)

The total energy operator is

 As the second derivative of a function is a measure of its curvature:

High curvature is associated with high kinetic energy,

Low curvature is associated with low kinetic energy.

Comparing the K.E of two particles based on curvature Distribution of K.E of a particle in space based on its
curvature
Understanding the K.E dependence on the curvature helps in interpreting the wave functions and predicting their
shapes.

For example, we have a wave function whose potential energy decreases with x and total energy remains constant.
So as the P.E decreases, K.E increases and the shape of the wave function could be predicted.

It can be observed that as the K.E increases, the

wavelength decreases.

This is in accordance with the de-Broglie relation between

momentum and wavelength.

p = as K.E increases, p increases.

λ
 Hermitian Operators

Operators and wavefunctions may be complex; however, eigenvalues of quantum mechanical operators must
be real because they are the only possible measured values, and measured values of observables are real. This
places a restriction on possible quantum mechanical operators. Operators that have the property that they
yield real eigenvalues are called Hermitian.

Hermitian operators follow the rule

• All Quantum mechanical operators corresponding to observables follow the ‘hermitian’ property.

• The operators and are Hermitian. (Derive)

• Eigenvalues of Hermitian operators are real i.e., ω = ω*

• Eigen functions of Hermitian operators are orthogonal. (Derive)

Common Operators
 Superposition of waves
For the wave function if A=B, ψ is not an eigenfunction of px

When the wavefunction of a particle is not an eigenfunction of an operator, the property (here, momentum) to which
the operator corresponds does not have a definite value.

In this specific case, we can still write cos kx as the linear combination of eikx and e-ikx, both of which are
eigenfunctions of px.

During multiple measurements, the particle goes with

momentum , half the time left side and half the time right side.
At a given instant we cannot predict in which direction the
particle is moving
 The same interpretation applies to any wavefunction written as a linear combination of eigenfunctions
of an operator (let us assume that it is px)

Linear combination of basis functions

where the ck are numerical coefficients and the ψk correspond to different momentum states.

According to quantum mechanics:

1. When the momentum is measured, in a single observation one of the eigenvalues corresponding to the ψk will
be found.

2. The probability of measuring a particular eigenvalue in a series of observations is proportional to the square
modulus (|ck|2).

3. The average value of a large number of observations is given by the expectation value, <Ω>, of the operator.