CH-231: Introduction to Quantum Chemistry

(3-0-0-6)

Postulates
 Postulates of Quantum Mechanics

Postulate 1: The concept of wave function

The state of a quantum system is completely
described by a function ψ(x, t) that depends
on the coordinates of the particles and time.
ψ(x, t) is called the wave function of the sys-
tem. ψ(x, t) has the important property that
the probability that the particle will be found
at time t in a spatial interval of width dx at x0
is given by ψ ∗ (x0 , t) ψ(x0 , t) dx.
 Postulates of Quantum Mechanics

Postulate 1: The concept of wave function

The state of a quantum system is completely
described by a function ψ(x, t) that depends
on the coordinates of the particles and time.
ψ(x, t) is called the wave function of the sys-
tem. ψ(x, t) has the important property that
the probability that the particle will be found
at time t in a spatial interval of width dx at x0
is given by ψ ∗ (x0 , t) ψ(x0 , t) dx.

ρ = ψ ∗ ψ is called the probability density

 Description

What is a wave function?

 Description

What is a wave function?

It is related to the probability of finding a par-

ticle at position x0 at time t0 .
 Description

What is a wave function?

It is related to the probability of finding a par-

ticle at position x0 at time t0 .

In QM, the physical meaning of the wave func-

tion is difficult to describe in that it can be
negative, complex, phase dependent, etc
 Description

What is a wave function?

It is related to the probability of finding a par-

ticle at position x0 at time t0 .

In QM, the physical meaning of the wave func-

tion is difficult to describe in that it can be
negative, complex, phase dependent, etc

Think of the wave function as simply a descrip-

tion of the system of interest, and with this de-
scription various properties of the system can
be determined (as we will see).
Can any function be a wave function?
Can any function be a wave function?

NO!
Can any function be a wave function?

NO!

Suitable function/well-behaved function

 Suitable function/well-behaved function

1
ψ has to be square-integrable: ψ must be
R∞ ∗
normalizable, ψ ψ dτ = 1 == h ψ|ψi
−∞
Examples: tan(x)? sin(x)?
 Suitable function/well-behaved function

1
ψ has to be square-integrable: ψ must be
R∞ ∗
normalizable, ψ ψ dτ = 1 == h ψ|ψi
−∞
Examples: tan(x)? sin(x)?
 Suitable function/well-behaved function

1
ψ has to be square-integrable: ψ must be
R∞ ∗
normalizable, ψ ψ dτ = 1 == h ψ|ψi
−∞
Examples: tan(x)? sin(x)?

i.e. Functions that can be normalized can serve as wave functions.

 Suitable function/well-behaved function

1
ψ has to be square-integrable: ψ must be
R∞ ∗
normalizable, ψ ψ dτ = 1 == h ψ|ψi
−∞
Examples: tan(x)? sin(x)?

i.e. Functions that can be normalized can serve as wave functions.

This implies that the wave function approaches zero as x approaches

infinity.
 Problem

Normalize the following wave function over the

2
interval −∞ ≤ x ≤ ∞: ψ(x) = A e−αx
Suitable function/well-behaved function

The wave function ψ has to be single valued

Suitable function/well-behaved function

The wave function ψ has to be single valued

NOT single-valued Single-Valued

Suitable function/well-behaved function

The function and its first derivative must be

continuous: smoothly varying functions with no
discontinuities
Suitable function/well-behaved function

The function and its first derivative must be

continuous: smoothly varying functions with no
discontinuities
 Suitable function/well-behaved function

The function and its first derivative must be

continuous: smoothly varying functions with no
discontinuities

Both ψ and ψ 0 are continuous unless the potential has

delta functions or infinite high walls in which cases
ψ 0 may have finite jumps.
Suitable function/well-behaved function

The wave function has to be finite.

 Problems

Which of the following is acceptable or not as

a state function
exp(x) (0, ∞)
exp(−x) (0, ∞)
exp(−x) (-∞,∞)
sin−1 (x), (-1,1)
f (x) = x2 +1
√
f (x) = ± x, x ≥ 0
1
Ψ = 4−x , 0 ≤ x ≤ 10
1
Ψ= 4−x
, 0≤x≤3
Problems
For an electron√ having a one-dimensional wave
function Ψ = 2sin πx in the range x= 0 to 1,
what is the probability that the electron is in
the first half of the range, i.e. within 0 to 0.5?
For an electron√ having a one-dimensional wave
function Ψ = 2sin πx in the range x= 0 to 1,
what is the probability that the electron is in
the first half of the range, i.e. within 0 to 0.5?
Rb ∗
Use 1
ψ ψ dτ = [ x2 − 4π sin 2πx]ba
a
Ans: 0.5
Experimental Observables Correspond to
Quantum Mechanical Operators

Postulate 2: To every observable in classical

mechanics, there corresponds a linear operator
in quantum mechanics. Since observables are
real, the operator is Hermitian.
 Operators

Observable Operator
Name Symbol Symbol Operation
Position x x̂ multiply by x

d
Momentum P P̂ −i~ dx
2 2
d
Kinetic energy T T̂ − 2m
~
dx2

Potential energy V V̂ multiply by V(x)

2 2
d
Total energy E Ĥ − 2m
~
dx2
+ V(x)
∂
Angular momentum lx = ypz − zpy L̂x −i~(y ∂z − z ∂∂y )

∂
ly = zpx − xpz L̂y −i~(z ∂x − x ∂∂z )

∂
lz = xpy − ypx L̂z −i~(x ∂y − y ∂∂x )
 Problems

Evaluate [P̂x , x̂] and [x̂2 , P̂x ]

Determine the commutator √ of the operators√a and
a , where a = (x̂ + ip̂)/ 2 and a† = (x̂ − ip̂)/ 2.
†
 Problems

Evaluate [P̂x , x̂] and [x̂2 , P̂x ]

Determine the commutator √ of the operators√a and
a , where a = (x̂ + ip̂)/ 2 and a† = (x̂ − ip̂)/ 2.
†

[Â, Â] =0
[Â + B̂, Ĉ] = [Â, Ĉ] + [B̂, Ĉ]
[Â, B̂ Ĉ] = [Â, B̂]Ĉ + B̂[Â, Ĉ]
A set of measurements on identically prepared
systems
Postulate 3: When a system is described by a
wave function ψ the mean value of the observ-
able  in a series of experiments is given by the
average value of the observable of Â,

R∞
ψ ∗ Â ψdτ
−∞
< Â >= R∞
ψ ∗ ψdτ
−∞
A set of measurements on identically prepared
systems
Postulate 3: When a system is described by a
wave function ψ the mean value of the observ-
able  in a series of experiments is given by the
average value of the observable of Â,

R∞
ψ ∗ Â ψdτ
−∞
< Â >= R∞
ψ ∗ ψdτ
−∞

Average value is also called as expectation value

 Expectation values

R∞
ψ ∗ Â ψdτ
−∞
< Â >= R∞
ψ ∗ ψdτ
−∞
 Expectation values

R∞
ψ ∗ Â ψdτ
−∞
< Â >= R∞
ψ ∗ ψdτ
−∞

If the wave function is normalized, then

 Expectation values

R∞
ψ ∗ Â ψdτ
−∞
< Â >= R∞
ψ ∗ ψdτ
−∞

If the wave function is normalized, then

Z∞
< Â >= ψ ∗ Â ψdτ
−∞
 Postulates of Quantum Mechanics

Postulate 4: The wave function of a system

evolves in time according to time-dependent
Schrödinger’s equation,
∂ψ(x, t)
Ĥψ(x, t) = i~
∂t