Lecture 4 – Mathematics for quantum

chemistry

The Born interpretation of wave function

A wave function gives the probability of finding the

Lecture 5: particle at a certain location.
The Meaning of Wave Function
This is the most commonly misunderstood concept in
quantum chemistry.

It is a mistake to think of a particle spreading like a cloud
according to the wave function. Only its probability
Dr. Truong Thanh Tu density does.
Department of Physical Chemistry, Faculty of Chemistry
19 Le Thanh Tong, Hoan Kiem, Hanoi
ttruong@hus.edu.vn

TTT 2017 Lecture 5/ 2

The Born interpretation The Born interpretation

The square of the wave function |Ψ|2 at a point is

What is a wave function? proportional to the probability of finding the particle at
that point.

It has all the dynamical information
about the particle.

More immediately, it has the 2
information about the location of the Ψ = Ψ *Ψ ≥ 0 Always real, non-negative
particle.
Complex conjugate of Ψ

Max Born 2
a + bi = (a + bi )* (a + bi) = ( a − bi )(a + bi )
= a 2 − b 2i 2 = a 2 + b 2 ≥ 0
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The Born interpretation The Born interpretation

One-dimension: if the wave

A wave function is in general function of a particle has the
complex. value Ψ at point x, the
probability of finding the particle

But |Ψ|2 is always real, non-
between x and x+dx is
negative.
proportional to |Ψ|2 dx.

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Lecture 4 – Mathematics for quantum
chemistry

The Born interpretation The Born interpretation

Three-dimension: the probability of finding the
particle in an infinitesimal volume dτ = dx dy dz at
point r is proportional to |Ψ(r)|2 dτ.

|Ψ(r)|2 is the probability density.

It is a mistake to think that a particle spreads like a cloud
or a mist with density proportional to |Ψ|2. (Such an
interpretation was seriously considered in physics but
was dismissed.)

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The Born interpretation Nobel Prizes in Physics

Many notable physicists resisted the Born interpretation
such as Erwin Schrödinger and Albert Einstein, the very
architects of quantum mechanics.

The strongest advocates were Max Born and Niels Bohr.
Today, we know that this is the correct interpretation.

1918 Planck – Quantization of energy

1920 Einstein – Photoelectric effect

1921 Bohr – Quantum mechanics

1927 Compton – Compton effect

1929 de Broglie – de Broglie relation

1932 Heisenberg – Quantum mechanics

1933 Schrödinger & Dirac – Atomic theory

1945 Pauli – Pauli principle

1954 Born – Born interpretation

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Normalization Normalization

When Ψ satisfies the Schrödinger equation
We are free to multiply any constant factor (other than
zero) to Ψ, without stopping it from the solution of the
 2
 Schrödinger equation.
HΨ = − ∇ 2 + V ( x , y , z )  Ψ = EΨ
Remembering that |Ψ|2dxdydz is only proportional to
 2 m  the probability of finding the particle in dxdydz volume at

so does NΨ, where N is a constant factor (x,y,z), we consider it the most desirable and convenient
if the wave function be normalized such that finding the
 2
 particle somewhere in the space is equal to 1.
H ( NΨ ) =  − ∇ 2 + V ( x , y , z )  ( NΨ ) = E ( NΨ )

 2m 

because this equation has Ψ in both right- and left-hand

sides.

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Lecture 4 – Mathematics for quantum
chemistry

Normalization Normalization

We multiply a constant to Ψ.

For these equations to be satisfied
Ψ ′ = NΨ
such that
∫
Ψ′ dx = N 2 ∫ Ψ dx = 1 ∫∫∫ Ψ′ dxdydz = N 2 ∫∫∫ Ψ dxdydz = 1
2 2 2 2

∫ Ψ′ dx = N 2 ∫ Ψ dx = 1 ∫∫∫ Ψ′ dxdydz = N 2 ∫∫∫ Ψ dxdydz = 1

2 2 2 2
we simply adjust N to be
1 1

These equations mean that probability of finding the N= N=
∫ dx ∫∫∫ Ψ dxdydz
2 2
particle somewhere is 1. After normalization, |Ψ|2dxdydz Ψ
is not only proportional but is equal to the probability of
finding the particle in the volume element dxdydz at
N is a normalization constant, and this process is
(x,y,z). called normalization.

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Dimension of Example
a wave function

Normalized wave functions in one and three dimensions
Normalize the wave function e–r/a . 0

satisfy

Hint 1: ∞ n!
∫Ψ ∫∫∫ Ψ ∫ x n e − ax dx =
2 2
dx = 1 dxdydz = 1
0 a n +1
where the right-hand side is dimensionless.
Hint 2:

Ψ has the dimension of 1/m1/2 (one dimensional) and
1/m3/2 (three dimensional).
∞ π 2π
∫∫∫ f ( x, y, z )dxdydz = ∫ ∫ ∫
Whole Space
0 0 0
f ( r , θ , φ )r 2 dr sin θdθdφ

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Hint 2 Example

The normalization constant is given by

∞ π 2π 1 1
∫∫∫ f ( x, y, z )dxdydz = ∫ ∫ ∫
Whole Space
0 0 0
f ( r , θ , φ )r 2 dr sin θdθdφ N=
∫∫∫ Ψ
2
dxdydz
=
∫∫∫ Ψ
2 2
r sin θdrdθdφ

∞ π 2π
∫∫∫ Ψ r 2 sin θdrdθdφ = ∫ e − 2 r / a0 r 2 dr ∫ sin θdθ ∫ dφ
2
0 0 0

2
= × 2 × 2π = πa03
( 2 / a0 ) 3
π
∫ sin θdθ = [− cos θ ]0 = 2
π
0

1 1
N= ; Ψ = Ne − r / a0 = e − r / a0 Dimension 1/m3/2
πa03 πa03
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Lecture 4 – Mathematics for quantum
chemistry

Normalization and Normalization and

time-dependent SE time-dependent SE

If Ψ is a normalized solution of time-independent SE,
Therefore, both Ψ and Ψeik correspond to the same time-
Ψeik for any real value of k is also a normalized solution independent system. In other words, a time-independent
of SE because wave function has inherent arbitrariness of eik where k is
any real number. For example, Ψ and –Ψ represent the
2 * same time-independent state.
(
Ψeik = Ψeik ) ( Ψe ) = ( Ψ e )( Ψe )
ik * − ik ik

Let us revisit time-dependent and independent
2 2
Schrödinger equations.
= Ψ e −ik eik = Ψ

The simplest example is when eiπ = –1. Ψ and –Ψ are
both normalized and with the same probability density
|Ψ|2.

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Time-dependent Time-dependent
vs. time-independent vs. time-independent

E
−i t
 2π   2π 
∂ ∂ i λ x−2πν t  i x−2πν t  Ψ ( x, t ) = Ψx ( x) Ψt (t ) = Ψx ( x)e
i
∂t
Ψ=i
∂t
e = i −i2πν e  λ ( ) 
Time-dependent Schrödinger equation

2 h
= −i 2πνΨ = hνΨ = EΨ ∂ ∂ ∂ −i E t
2π HΨ(x,t) = i Ψ(x,t) = Ψ x (x)i Ψ t (t) = Ψ x (x)i e
∂t ∂t ∂t
= EΨ x (x)Ψ t (t) = EΨ(x,t)

∂ ∂ −i E t  E  −i E t Time-independent Schrödinger equation

i Ψ =i e = i  −i  e = EΨ
∂t ∂t   If we substitute the wave function into time-dependent equation
we arrive at time-independent one.
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Normalization and Time-dependent

time-dependent SE vs. time-independent

E

This means even though this wave function has −i t
apparent time-dependence Ψ ( x, t ) = Ψx ( x)Ψt (t ) = Ψx ( x)e

E
−i t
Ψ ( x, t ) = Ψx ( x)Ψt (t ) = Ψx ( x)e
it should be representing time-independent physical state.
E

In fact e −i t (which we call “phase”) is viewed as the
arbitrariness eik. Probability density is

E 2
2 −i t 2 Essentially
Ψ ( x, t ) = Ψx ( x)e = Ψx ( x ) time-independent!

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Lecture 4 – Mathematics for quantum
chemistry

What is a “phase”? Allowable forms of

wave functions
E
−i t
Ψ ( x, t ) = Ψx ( x)Ψt (t ) = Ψx ( x)e
The Born interpretation: the
square of a wave function is a
probability density.

This immediately bars a wave
function like figure (c), because
a probability should be a unique
value (single valued)

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Allowable forms of Allowable forms of

wave functions wave functions

Apart from the Born interpretation,

Probability should add up to unity, the form of the Schrödinger
when all possibilities are included. equation itself set some
Square of a wave function should conditions for a wave function.
integrate to unity.

This bars a function like (d)  2 d2 
ĤΨ =  − + V̂ (x) Ψ = EΨ
because it integrates to infinity 2
regardless of any nonzero
 2m dx 
normalization constant (square
The second derivatives of a wave
integrable). function must be well defined.

∫ Ψ′
2
dx = 1
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Allowable forms of Allowable forms of

wave functions wave functions

For the second derivative to exist,
For the second derivatives to be

the wave function must be nonsingular, the wave function
continuous, prohibiting a should usually be smooth,
function like (a) which is discouraging a kinked function like
(b).
discontinous.

There are exceptions. When the

It is also impossible to imagine a potential V also has a singularity,
system where the probability a kinked wave function is
density changes abruptly. possible.

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Lecture 4 – Mathematics for quantum
chemistry

Existence of first and Summary

second derivatives

The Born interpretation relates the wave function to the

probability density of a particle.

A wave function can be normalized such that square of
it integrates to unity (100 % probability of finding a
particle somewhere).

A wave function should be single-valued, square-
integrable, continuous, and (smooth)*.

*Exceptions exist.
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