ec a c (He e be g 1925 ed a e e a a ec a c ).

c n e ai e e , The
e e eSchrödinger
g ac a , aEquation
d e (1926)
e-de e de fac f E
e ace- fac ( a e Se a a i n f Va iable ec e d c ed Sec 2.2)
• The central equation in Quantum Mechanics.
• Observable = total energy of system.

e Schrödinger
e a a ef c de e de ( e- deHamiltonian
e de )Operator
a ef c a d
Equation Ĥψ = Eψ Ĥ
a E a a d ca ce g e e e a fac , e ba
E Total Energy
a : ˆ =T ˆ +V ˆ and E = T + V.
where H

• SE can be set up for any physical system.

• The form of Ĥ depends on the system.
• Solve SE Þ y and corresponding E.

e ea f f eE a a e ec ed a e e
M f a ca f a ec a c c e be ba ed
ec c ). T e e f e e- de e de Sc d ge e a ca e be e
 Time-Dependent Schrodinger Wave Equation

@ ~2 @ 2
i~ (x, t) = (x, t) + V (x) (x, t)
@t 2m @x2
Total E term K.E. term P.E. term
PHYSICS
NOTATION
iEt/~
(x, t) = e (x)
Time-Independent Schrodinger Wave Equation

~2 @ 2
E (x) = (x) + V (x) (x)
2m @x2
 Wavefunctions
• In QM, a “particle” is distributed in space like a wave.
• We cannot define a position for the particle.
• Instead we define a probability of finding the particle at any point in space.

• Wavefunction (y) – a wave representing the spatial distribution of a “particle”.

• Represents the amplitude of the still vaguely defined matter waves

• |y(x)| – the magnitude of y at point x.

• Because y may be imaginary or complex Þ y2 would be negative or complex.
• For the general case, where y is complex (y = a + ib) then:
|y|2 = y*y where y* is the complex conjugate of y.
i = -1
probability density (y* = a – ib)
 Particle Wavefunctions: Examples
Examples of y(x)

y(x) y(x) y(x)

x x x

The corresponding probability distributions |y(x)|2 of these states are:

|y|2 |y|2 |y|2

x x x
Key point: Particle cannot be associated with a specific location x.
 Wavefunctions

The Importance of y

• y completely defines the system (e.g. electron in an atom or molecule).

• If y is known, we can determine any observable property (e.g. energy, vibrational

frequencies, …) of the system.

• QM provides the tools to determine y computationally, to interpret y and to use y to

determine properties of the system.
Condition of the Acceptable Wavefunction

The Born interpretation of places restrictions on the form of the

wavefunction:

SCFN
(a) must have a single value at any point in space;

(b) must be continuous (no breaks);

(c) The gradient of (d /dx) must be continuous (no kinks);

(d) must be finite everywhere;

(e) cannot be zero everywhere.

Other restrictions (boundary conditions) depend on the exact system.

These restrictions on mean that only certain wavefunctions and only certain energies of the system
are allowed.
Quantization of Quantization of E
 Wavefunctions
The Born Interpretation (1926)

“The square of the wavefunction at any point in space is proportional to the probability of finding
the particle at that point.”

Example: 1-D System

If the wavefunction at point x is y(x), the probability of finding the particle in the
infinitesimally small region (dx) between x and x+dx is:

P(x) µ |y(x)|2 dx
 Normalization of the Wavefunction

P(r) µ |y(r)|2 dt
• What is the proportionality constant?
• If y is such that the sum of |y(r)|2 at all points in space = 1, then:
P(x) = |y(x)|2 dx 1-D
P(r) = |y(r)|2 dt 3-D

• As summing over an infinite number of infinitesimal steps = integration, this means:

¥ 2
Ptotal (1D ) = ò ψ(x ) dx = 1
-¥

¥ 2 ¥ ¥ ¥ 2
Ptotal (3D ) = ò ψ(r ) dτ = ò ò ò ψ(x, y, z ) dxdydz = 1
-¥ -¥ -¥ -¥

• i.e. the probability that the particle is somewhere in space = 1.

• In this case, y is said to be a normalized wavefunction.

How to Normalize the Wavefunction

2
• If y is not normalized, then:
ò ψ(r ) dτ = A ¹ 1

• A corresponding normalized wavefunction (yNorm) can be defined:

1
ψ Norm (r ) = ψ(r )
A

such that: 2

ò ψ Norm (r ) dτ = 1

• The factor (1/ÖA) is known as the normalization constant (sometimes represented by N).
 C e de ce P c e
Hamiltonian Operator C e de ce P i ci le B

• Wavefunction (y) contains all the information we need to know about any particular system.
I M
• How do we determine y and use it to deduce properties of the system?
.I

Operators and Observables . ,

E
• If y is the wavefunction representing a system, we can write: , (
( ).
Q̂ψ = Qψ
C O ea
A ,
where Q – “observable” property of system (e.g. energy, momentum, dipole moment …) .
Li ea M me m:
Q̂ – operator corresponding to observable Q. ( -

d/dx (eax) = a eax

:
d2/dx2 (sin ax) = -a2 sin ax
P ii
)* = ) ( - )

Operator for position in the x- Operator for linear momentum in the x-direction: (
#"! = −&ℏ
direction is just multiplication by x : ()
Constructing Kinetic and Potential Energy QM Operators
1. Write down classical expression in terms of position and momentum.
2. Introduce QM operators for position and momentum.

Examples
1. Kinetic Energy Operator in 1-D T̂x
px2 ˆ x2
ˆT = p ! 2 æç d 2 ö
CM Tx = Þ QM =- ÷
2m çè dx 2 ÷
x
2m 2m ø
2. KE Operator in 3-D T̂ “del-squared”

2 2
p2 px + py + pz
2 ˆ2
ˆT = p ! 2 æç ¶ 2 ¶2 ¶2 ö
÷=- ! 2
T= = =- + + Ñ2
CM 2m 2m QM 2m 2m çè ¶x 2 ¶y 2 ¶z 2 ÷
ø 2m

partial derivatives
operate on y(x,y,z)
3. Potential Energy Operator V̂ (a function of position)
\ PE operator corresponds to multiplication by V(x), V(x,y,z) etc.
Examples

1. Particle Moving in 1-D y(x)

ˆ ψ=T
ˆ ψ+V
ˆ ψ = Eψ ! 2 æç ¶ 2 ψ ö÷
H - + V(x )ψ = Eψ
2m çè ¶x 2 ÷ø

• The form of V(x) depends on the physical situation:

– Free particle V(x) = 0 for all x.
– Harmonic oscillator V(x) = ½kx2

2. Particle Moving in 3-D y(x,y,z)

• SE Þ ! 2 æç ¶ 2 ψ ¶ 2 ψ ¶ 2 ψ ö÷
- + + + V(x, y, z )ψ = Eψ
2m çè ¶x 2 ¶y 2 ¶z 2 ÷ø
!2 2
or - Ñ ψ + V(x, y, z )ψ = Eψ Note: The SE is a second
2m order differential equation