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CHEM F111 General Chemistry Lecture 04

Wave-equation, wavefunction, operators and
quantum description of simple systems
 Review of lecture 03

• Wave-particle duality; Uncertainty principle

• Wavefunction – definition and interpretation
• Time-dependent Schrödinger equation

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 Postulates of quantum mechanics
(revision)

Postulate 1:

The state of a quantum-mechanical system is completely specified by a

function Ψ(x1,y1,z1,….xN,yN,zN, t),
t) that depends on the coordinates of all the
particles and on the time. This function, known as the wavefunction of the
system, has important property that |Ψ|2dτ=(Ψ
τ= *Ψ)dτ, (where,
dτ=dx1dy1dz1...dxNdyNdzN) represents the probability that the particle 1 is
in volume element dx1dy1dz1 surrounding (x1,y1,z1), particle 2 is in the
volume dx2dy2dz2 surrounding (x2,y2,z2), and so on, at the instant, t.
(Born interpretation)

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 Postulates of quantum mechanics
(revision)

Postulate 2:
To every observable in classical mechanics, there corresponds an
operator in quantum mechanics.

Postulate 5:
The wavefunction of a system evolves in time according to the time-
dependent Schrödinger equation.

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 Wavefunction: one-particle system in 1D
(revision)
We have obtained: i
ℏ ( p x⋅x−E⋅t )
Ψ ( x ,t )= A e

We now study the spatial dependence of the function:

i
∂ Ψ = A e ℏ ( p ⋅x− E⋅t ) i p = i p Ψ
x
p^ Ψ=
ℏ ∂
Ψ
ℏ x ℏ x x
∂x i ∂x
ℏ ∂
px =
^ (Momentum Operator defined)
i ∂x
Taking the second derivative wrt x, it follows
2
2
∂ Ψ =− x Ψ p 2 2 ∂
2

2 2
p x Ψ=−ℏ 2
Ψ
∂x ℏ ∂x
Consequently, we have

p2x 2
ℏ ∂2
=− (K.E. Operator defined)
2m 2 m ∂ x2

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 Wavefunction: one-particle system in 1D
(revision)
We have obtained: i
ℏ ( p x⋅x−E⋅t )
Ψ ( x ,t )= A e
Next, we study the temporal dependence of the function:
i
∂ Ψ = A e ℏ ( p ⋅x− E⋅t ) −i E= 1 E Ψ
x
^ Ψ=i ℏ ∂ Ψ
E
∂t ℏ iℏ ∂t
^ ℏ ∂
E=i (Total energy operator*)
∂t
Let V(x) be the potential energy operator.
ℏ ∂2 Ψ ^ ∂Ψ
It then follows: − + V ( x ) Ψ =i ℏ
2 m ∂ x2 ∂t
^ Ψ = i ℏ ∂ Ψ (Time-dependent Schrödinger equation)
H
∂t

The time dependent Schrödinger equation describes time evolution of the

system
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Variable separation
(one particle system in 1D)
2 2
We have − ℏ ∂ Ψ ( x ,t ) ^ ∂ Ψ ( x ,t )
2
+ V ( x ) Ψ ( x , t )=i ℏ
2m ∂x ∂t
Suppose it is possible to express the wavefunction as Ψ ( x ,t )=ψ( x) ϕ(t )
Then, by variable separation method, one can solve and obtain
2 2
H^ ψ= E ψ , that is : − ℏ d ψ ^
+ V ( x) ψ=E ψ
2 m dx 2
This is (1D) time-independent Schrödinger equation. (Note that this is
possible because the Hamiltonian operator is time-independent in this case).
dϕ
The time-dependent part gives: i ℏ =E ϕ ⇒ ϕ (t )=e−iEt /ℏ
dt
What will be the probability density in such a case?

|Ψ ( x , t )|2 =Ψ ( x ,t )∗ Ψ ( x , t )
=ψ ( x)∗ ψ( x) ϕ(t )∗ ϕ (t )=ψ( x)∗ ψ( x) eiEt / ℏ e−iEt /ℏ =|ψ( x)|2

The probability density (and hence, the probability) turns out to be time-
independent! Such a state is said to be a stationary state.
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Probability Density

Probability
density │ψ │2
is physically
significant

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Normalization

• The total probability of finding the system (particle) in space is

obtained by integrating the probability density over the volume
element, spanning the volume enclosed by the boundaries.
∞
• Total probability ∗
Ψ Ψ d τ=N
∫
−∞

• The value of N should be positive definite, so that Ψ can be scaled

by a factor of N-1/2, so that the total probability is scaled to unity.
This procedure of scaling is known as normalization.

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Well-behaved wavefunction

A function is said to be well-behaved when it satisfies following

conditions:

• The wavefunction should be finite and single-valued.

• The wavefunction and its first derivative should be continuous
everywhere.
• The wavefunction and its first derivative should be differentiable
everywhere (except maybe at a point where the potential goes to
infinity).
• The wavefunction should die at boundaries.
• The wavefunction should be quadratically integrable
(normalizable).

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Operators

Operator is a mathematical instruction or rule that when acts on a

function, transforms it to another function.
e.g. let an operator A be “derivative wrt x” operator. Then,
A f(x) = g(x); where g(x)= df/dx
Multiplicative operators simply multiply the function e.g. position
operator, potential energy operator, etc.
Operators can have more complicated form (e.g. sum of two or more
operators – e.g. Hamiltonian operator)

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Eigenvalue equations

Let us consider another example.

Consider an operator: “first derivative wrt x”:

(d/dx)emx = memx;

(d/dx)sin(kx)=k cos(kx); (d/dx)cos(lx)=-l sin(lx);

In these cases; emx, is an eigenfunction of the operator (d/dx), with the

eigenvalue m, but the functions, sin(lx) and cos(kx) are not.

What about the function: cos(ky)sin(z)e-mx ? Is it an eigenfunction of

the operator (d/dx)?

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Eigenvalue equations
A function f(x) is said to be eigenfunction of an operator if the
action of the operator on the function gives the original function
multiplied by a constant.
The constant is said to be an eigenvalue of the operator and the
equation is known as eigenvalue equation. e.g. Consider an operator:
“second derivative wrt x”:

(d2/dx2)emx = m2emx;

(d2/dx2)sin(kx)=-k2sin(kx);

(d2/dx2)cos(lx)=-l2cos(lx);
In these cases; emx, sin(kx), cos(lx), are all eigenfunctions of (d2/dx2),
with the eigenvalues m2, -k2 and -l2, respectively.
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Eigenvalue equations

2
−nx
Homework: Show that e (where, n is a constant) is an
eigenfunction of the operator:

d2 d
2
+2 nx
dx dx

What is the eigenvalue?

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Postulates of quantum mechanics

Postulate 3:
In any measurement of the observable associated with the an operator, Â, the
only values that will ever be observed are the eigenvalues, a, which satisfy
the eigenvalue equation: ÂΨ=aΨ.
When an operator operates or acts on a function, the physical interpretation of this is probing the system
to measure the corresponding observable. Initially, the system may be in some random, state. However,
when we probe to measure the observable, the probe disturbs the system and projects it to one of its
characteristic states – the eigen states of the operator. In the postulate given above, the state, Ψ, is the state
in which the system has reached after the probe is applied (and not necessarily, before its application). In
other words, the action the operator, Â has taken the system to the state, Ψ, which is the eigen state of the
operator and the eigenvalue a is obtained. At this moment, since the system has already reached in the
eigen state of Â, its further action without any time-lag would keep the state of the system unaltered and
would return the eigen value, a.

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Observables and properties

Consider the (time-independent) Schrödinger equation:

H^ ψ= E ψ → Eigenvalue equation
If ψ is normalized it can be easily proven that ^ ψd τ
E=∫ ψ∗ H

∫ ψ∗ H^ ψ d τ
If ψ is not normalized, we can write E=
∫ ψ∗ ψ d τ

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Observables and properties

Consider the (time-independent) Schrödinger equation:

H^ ψ= E ψ → Eigenvalue equation
If ψ is normalized it can be easily proven that ^ ψd τ
E=∫ ψ∗ H

∫ ψ∗ H^ ψ d τ
If ψ is not normalized, we can write E=
∫ ψ∗ ψ d τ
The Hamiltonian operator represents total energy of the system, so in the above
expression, the observable quantity we get is energy. If the wavefunction in the
above expression is not an eigenfunction of the Hamiltonian operator, then,
instead of exact energy, we obtain average energy.

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Observables and properties

Consider the (time-independent) Schrödinger equation:

H^ ψ= E ψ → Eigenvalue equation
If ψ is normalized it can be easily proven that ^ ψd τ
E=∫ ψ∗ H

∫ ψ∗ H^ ψ d τ
If ψ is not normalized, we can write E=
∫ ψ∗ ψ d τ
The Hamiltonian operator represents total energy of the system, so in the above
expression, the observable quantity we get is energy. If the wavefunction in the
above expression is not an eigenfunction of the Hamiltonian operator, then,
instead of exact energy, we obtain average energy.
If the Hamiltonian operator is replaced by some other operator and if the
wavefunction does not happen to be the eigenfunction of that operator, then the
average value of the corresponding observable will obtained.
∫ ψ∗ A^ ψ d τ
⟨ A ⟩=
∫ ψ∗ ψ d τ
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Postulates of quantum mechanics

Postulate 4:
If a system is in a state described by a wavefunction Ψ, then the average
value of an observable, Ŷ is given by
∗ ^

⟨Y ⟩=
∫ Y Ψdτ
Ψ
∗
∫Ψ Ψd τ

In this case, the state, Ψ, is a non-eigenstate of the operator, Ŷ.

Had Ψ been an eigenstate of Ŷ, then instead of the average value, one
would obtain the eigenvalue of Ŷ corresponding to the eigenstate, Ψ.

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