Lecture 2

Lecture 2
The Wave Function
Study Goal of This Lecture
• Time-independent Schrödinger Equation.
• Requirements of wavefunctions.
2.1 Time-Independent Schrödinger Equation
Last lecture we discussed the consequences of the wave-particle duality and fi-
nally reach the point to introduce the time-independent Schrödinger equation(T.I.S.E.):
~2 2
− ∇ ψ(~r) + V (~r)ψ(~r) = Eψ(~r). (2.1)
2m
All stationary states of a particle under the influence of potential V (~r) must satisfy
this equation. Q: Why the station-
ary state of a parti-
2.1.1 Hamiltonian operator cle must satisfy the
Note that we can further identify on the left hand side of the Schrödinger equa- T.I.S.E. ?
tion:
energy,
a real number
~2 2 z}|{
{− ∇ + V (~r)} ψ(~r) = E ψ(~r), (2.2)
| 2m {z }
something acting
on the wavefunction
1
we can define an “operator” called “Hamiltonian”
~2 2
Ĥ = − ∇ + V (~r). (2.3)
2m
d
e.g. for dx ,
d 2
dx (x ) = 2x
operator: acting on a function to generate a different function.
operand: the subject of an operator.
Here Ĥ is an operator that is related to the total energy of the system. With Ĥ, we
can rewrite the Schrödinger equation as:
Ĥψ(~r) = Eψ(~r). (2.4)
This is a different yet equivalent way to write the time-independent Schrödinger

equation. ψ(~r) that satisfies Ĥψ(~r) = Eψ(~r) is a stationary wave function. Normally,
one can find infinite-number of wave functions(states) that satisfy the T.I.S.E.
Notice that solving Schrödinger equation is to find wave functions that when
“operated” by Ĥ, yield the same functions with a real proportional constant. This
kind of equation posts an “eigenvalue problem”.
When Ĥψ(~r) = Eψ(~r), we say ψ(~r) is an eigenfunction of Ĥ and E is the eigen-
value. Solving time-independent Schrödinger equation is to find the eigenfunctions
of the Hamiltonian operator Ĥ.
Ĥψn (~r) = En ψn (~r). (2.5)
In Equ (2.5), ψn (~r) is the eigenfunction of Ĥ and En is the eigenvalue associate

with ψn (~r). We normally can find infinite number of solutions. Such eigenvalue
problems are not at all difficult to understand.
d
• eigenfunction of dx ?
d2
• eigenfunction of dx2
?
• ......
observable ↔ operator
Quantum mechanics concern many operators. Actually each classical physical energy ↔ Ĥ
observable corresponds to a quantum operator.
2
Operators are central in quantum mechanics, actually, each physically measur-
able quantity has an operator associated with it, for example: we have identified the
operator for energy ⇒ Hamiltonian.
~2 2
Ĥ ←→ − ∇ + V (~r).
2m
Note
p̂2
Ĥ = T̂ + V̂ = + V̂ ,
2m
therefore we can identify
Ĥ ←→ V (~r)· [multiply by V (~r)],
∂
p̂x ←→ −i~ ,
∂x
r̂ ←→ ~r· [multiply by V (~r)].
From here we can construct operators for any observables in quantum mechanics.
We will elaborate this point in the next class when we discuss about operators.
2.1.2 Correspondence Principle
The “correspondence principle” provides a standard procedure to write down a

quantum operator from the definition of its classical counterpart.
1. Find expresion for the observable in terms of p and x. e.g. ~l = ~r × p~
2. Replace ~r ↔ r̂ , p~ ↔ p̂. e.g. L̂ = r̂ × p̂
2.2 Requirements of Wavefunctions
2.2.1 Max Born’s interpretation
The key subject in Schrödinger equation is ψ: the wave function. Max Born
pointed out that ψ does not have any physical meanung, and it is just a mathemat-
ical object that allows us to calculate experimentally measurable quantities. On the
other hand, the absolute square of ψ has a physical interpretation:
3
The probability of finding the particle in an infinitesimal volume (dτ = dxdydz)
at ~r is given by ψ ∗ (~r)ψ(~r)dτ ≡ |ψ(~r)|2 dτ .
Thus, |ψ(~r)|2 is the probability density of finding the particle at ~r.
1 3
(Note the dimension of ψ(x) is L− 2 in 1-D and L− 2 in 3-D.)
Thinking:
Note that probability of finding
|ψ(x)|2 : probability density someone in this class
who is “exactly” 20
|ψ(x)|2 dx : probability of finding the particle between x and x + dx
years old ← What do we
It is important to seperate probability density from probability.
normally mean by age =
20? A range!
Figure 2.1: Probability density
In order to fulfill this probability interpretation, a physical admissible wavefunc-

tion should satisfy the following conditions:
1. continuous everywhere in space. (i.e. finite p̂)
2. finite at any position.

These conditions
3. single-valued for all ~r
will be used to solve
R∞
4. −∞ |ψ(x)|2 dx = 1 (1-D) T.I.S.E..
R∞ R∞ R∞
r)|2 dτ
−∞ −∞ −∞ |ψ(~ = 1 (3-D)
normalization condition.
5. lim ψ(x) = 0
x→±∞
4
Also, for two wavefunctions, ψi and ψj ,
Z
if ψi∗ ψj dτ = 0 ⇒ orthogonal. (2.6)
Z
if ψi∗ ψj dτ = δij ⇒ orthornormal. (2.7)
R∞
 −∞ ψ1 ψ2 dx
0 for i 6= j ≡ inner product,

δij = , Kronecker delta. (2.8)
1

for i = j more contents would
show up in Lecture 3.

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The Wave Function

Study Goal of This Lecture

• Time-independent Schrödinger Equation.

2.1 Time-Independent Schrödinger Equation

Ĥψ(~r) = Eψ(~r). (2.4)

This is a different yet equivalent way to write the time-independent Schrödinger

Ĥψn (~r) = En ψn (~r). (2.5)

In Equ (2.5), ψn (~r) is the eigenfunction of Ĥ and En is the eigenvalue associate

Ĥ ←→ V (~r)· [multiply by V (~r)],

2.1.2 Correspondence Principle

The “correspondence principle” provides a standard procedure to write down a

1. Find expresion for the observable in terms of p and x. e.g. ~l = ~r × p~

2. Replace ~r ↔ r̂ , p~ ↔ p̂. e.g. L̂ = r̂ × p̂

2.2 Requirements of Wavefunctions

2.2.1 Max Born’s interpretation

Figure 2.1: Probability density

In order to fulfill this probability interpretation, a physical admissible wavefunc-

1. continuous everywhere in space. (i.e. finite p̂)

2. finite at any position.

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