Overview of QM

Statics

(r, t ) (r ) (t )

)
H n (r ) En n (r )
M.O. Calculations, Spectroscopy, and
Q. Stat. Mech.

Dynamics

H (r, t ) ih (r, t )
dt

(r, t ) (0)eit (r )

(r, t ) U ( ) (r, t )
Mol. dynamics, Q. Comp., Laser Pulse
Methods,2D NMR, and SS NMR, and
spectroscopy.

2
)

h

V (r )
H K V (r )

2m

Translational Motion Cartesian

2

2m

P. in Box
ex) STM, Devices

Rotational Motion

Spherical Polar

h
H
L L
2I

Rigid Rotor
Angular Mom.
&Spin
ex) FTS, NMR

Harmonic Motion

Centre of Mass

h
k

H
(r req ) 2
2
2

Vibrations
ex) IR, Raman

Quantum Mechanics for Many Particles

(r1 , r2 , r3 ,..., rk , t ) (r1 , t ) (r2 , t ) (r3 , t )... (rk , t )

(ri , t ) (ri )i (t )

)
H n (r1 , r2 , r3 ,..., rk ) En n (r1 , r2 , r3 ,..., rk )

m1
z1

r1
m2
z2

r2

h

V (r , r )
H

i
i
ij i
j
i 2mi
i, j
2
zi z j e

Vij (ri , r j )
r rj
2 i
4 o ri r j

m3
z3

r3
r4
(0,0,0)

m4
z4

En Energy Levels n Wavefuntions

Electronic Structure of Mols.

Properties of the Wavefunction

( x, t ) ( x) (t )
Single Valued

Finite and continuous

(t ) (0)e it
Complex Valued

ro

o
(0)

t
(t ) R
e

Im

( x , t ) dx

( x, t )
2

( x, t )
14_01fig_PChem.jpg

The Wavefunction in 3D
(ri , t ) (r xi , yi , zi ) )i (t )
(ri , t ) 3

(ri , t )

(ri , t ) dvi

Cartesian Coordinates

ri xi i yi j zi k

dv i d x i d y i d z i
Spherical Polar Coordinates

ri ri sin i cos i i
ri sin i sin i j
ri cosi k

dvi ri 2 sin i dri di di

14_01fig_PChem.jpg

Probability Distribution
(r, t )

z z* z z

Recall

(r, t ) * (r, t ) (r, t )

Probability of finding the particle at
exactly r, as a function of time.

P(r, t ) * (r, t ) (r, t )

P ( R, t )

xj yj zj

rj

xi yi zi

ri

P(r, t ) dv P(r, t ) dv

P (r, t ) dv
R

* (r, t ) (r, t ) dv
R

Probability of finding the particle

between ri and rj, defining the region
R, as a function of time

Probability Distribution and Time

P( R, t ) * (r, t ) (r, t ) dv
R

(r ) (t ) (r ) (t ) dv
*

(t ) (r ) (r ) dv (t )
R

(t )* P ( R) (t )
*

P ( R ) (r )* (r ) dv
R

(t )* (t ) P( R )
(0)* eit (0)e it P( R ) P ( R)

Probability is independent
of time!

Probability Distribution of Wavefunctions

Pn ( R, t ) Pn (r, t ) dv *n (r, t ) n (r, t ) dv n* (r ) n (r ) dv

= Pn ( R )
Re( ( x, t ))

P( x)

Probability of finding a
particle in a given interval is
independent of time and is
determine only by the r
Measurements are usually an
average over a long time on
the quantum mechanical time
scale and often reflect an
average over a large number of
particles.
In most experiments the
wavefunctions are incoherent.

Normalization of Wavefunctions
The probability of finding a particle in all space, S, must be 100 %.

Pn ( S , t ) *n (r, t ) n (r, t ) dv = 1
S

P ( S ) n* (r ) (r ) dv = 1
S

Therefore wavefunctions must be normalized.

If

n ( x, t )

is a solution to the Schrdinger equation it must be normalized.

n ( x, t )

n ( x, t )

n ( x, t )

N
*n ( x, t ) n ( x, t ) dv

N is the normalization constant.

Probability Distributions and Averages

Observed Distribution of Measurements

Normal Distribution

P(x)

N measurements, xi, with ci repeats, of k possible outcomes.

1 k
x ci xi
N i1

ci
P ( xi ) ci
N

For continuous P ( x) c ( x )
variables

c
i 1

c( x)
R

x P ( xi ) xi

P( x ) 1

x P ( x ) x dx

P( x) dx 1

i 1

i 1

Expectation Values
Measurements are
averages in time and
large number of particles
of observables.

x Pn ( x) x dx ( x, t ) ( x, t ) x dx
*
n

*
n

n ( x) n (t ) n ( x) n (t ) x dx
*

( x) n ( x) x dx n* (t ) n (t )
R

*
n

( x) x n ( x) dx

*
(
t
)
n (t ) 1
n

*
n

n* ( x) x n ( x) dx x

Expectation value of x.

O n* ( x)O n ( x) dx
R

Every observable has a

corresponding operator

14_01tbl_PChem.jpg

Operator Algebra
Linearity

[af ( x) bf ( x)] aO
f ( x ) bO
f ( x)
O
Analogy

Addition

bP ] f ( x) aO
f ( x) bP f ( x)
[ aO
Analogy

Association

f ax bx af ( x) bf ( x)

af

bg ( x ) af ( x ) bg ( x )

f ( x) O

OPQ

Analogy

f ( x)
P Q

fgh( x) f g h x

Commutation
Commutation

f ( x) PO
f ( x)
OP

Order matters !!!

Translation then rotation or rotation then translation

Commutator

PO
, P f ( x)
f ( x)
OP
O

, P ] 0 OP
PO
Operators Commute
if [O
, P ] 0 OP
PO

if [O

Operators Do Not
Commute

Commutation
Ex) Position and Momentum

x p x x ( x)
x , p x ( x) xp
x ( x) p x x ( x)
xp

d
x ih ( x) ih
x ( x)
dx

dx
d ( x) d

i h x
x ( x)
dx
dx

d ( x) dx
d ( x)
i h x
( x)
x i h ( x )
dx
dx
dx

x , p x ih 0

Properties of Hermitian Operators

For matrices

AT * A

For functions
*
( x) dx ( x) A
* * ( x) dx

(
x
)
A

( x) a ( x)
A
n
n n

* * ( x) a* * ( x)
A
n
n n

LHS

*
( x) dx * ( x)a ( x) dx a * ( x) ( x) dx

(
x
)
A
n n
n
n
n n n
n

RHS

an

* * ( x) dx ( x)a* * ( x) dx a* ( x) * ( x) dx

(
x
)
A
n
n n
n
n
n n n
an*

a an an
*
n

Properties of Hermitian Operators

Consider two eigenfunctions of A with different eigenvalues:

( x) a ( x)
A
m
m m

( x) a ( x)
A
n
n n
If A is Hermetian then:

*
*

(
x
)
A

(
x
)
dx

(
x
)
A

n
m ( x ) dx

n
*
m

LHS

*
( x) dx * ( x)a ( x) dx

(
x
)
A
n
m
m n n

an m* ( x) n ( x) dx

RHS

*
*
*
*

(
x
)
A

(
x
)
dx

(
x
)
a

m
n
n m m ( x) dx

am n ( x) m* ( x) dx

Properties of Hermitian Operators

an m* ( x) n ( x) dx am n ( x) m* ( x) dx 0

(an am ) m* ( x) n ( x) dx 0
m* ( x) n ( x) dx n ,m when an am n, m
Orthonormal set

m* ( x) n ( x) dx 0
Not orthogonal

when an am
Degenerate eigenvalues

Superposition Principle

)
H n (r ) n n (r )

Eigen Value

Eigen Relationship

n (r )

Set of Eigenfunctions

Consider m (r ) and n (r ) share the same eigenvalue En=

Em = E

Any linear combination of eigenfunctions of degenerate eigenvalues is an

eigenfunction:

)
)
)
H a n (r ) b m (r ) Ha n (r ) Hb m (r )
)
)
aH n (r ) bH m (r )

a n n (r ) b m m (r )
a n (r ) b m (r )
a n (r ) b m (r )

The Momentum Operator is Hermitian

?

* *

(
x
)
p

(
x
)
dx

(
x
)
p
( x) dx

d
S ( x)p ( x) dx ( x) ih dx ( x) dx
*

d
ih ( x) ( x) dx
dx

Integration by parts
b

u dv uv
a

b
a

vdu
a

d
where u ( x) & dv ( x)dx
dx
*

d *
du ( x)dx & v ( x)
dx

The Momentum Operator is Hermitian

d
d *
*
ih ( x) ( x) dx ih ( x) ( x) ih ( x) ( x) dx

dx
dx

wavefunctions are
finite and therefore
converge to zero as
x goes to infinity

d *
ih(0 0) ih ( x) ( x) dx
dx

d
( x) ih * ( x) dx
dx

* *

(
x
)
p
( x) dx

p ( x) is Hermetian

Operators with Simultaneous Eigenfunctions Commute.

( x) a ( x)
A
n
n n

B n ( x) bn n ( x)

, B ( x)
BA
( x)
A
AB
n
n

( x) BA
( x) A
b ( x) B a ( x)
AB
n
n
n n
n n
( x) a B ( x)
bn A
n
n
n

bn an n ( x) anbn n ( x)
bn an anbn n ( x )
0

, B 0 AB
BA
( x) BA
AB
( x)
A
n
n

Order of operations does not matter only if A and B commute.

Description of a Quantum Mechanical System

n (r, t ) n (r )n (t )

)
H n (r ) n n (r )

State

Energy Level

n Quantum number

3
2
1
0
0

3 (r )
2 (r )

1st excited State

Ground State

1 (r )
0 (r )

(t )
H

( x) (t ) dx
* ( x) * (t ) H
S

( x) dx
n ( x)* H
n
S

n ( x)* n n ( x) dx n
S

Energy levels are independent of time.

Eigenfunctions are stationary states.

n (r, t ) U ( ) n (r, t ) ein n (t ) n (r )

The system stays in the

same state, even though
the phase of the function
is time dependent.

Expectation Values Revisited

( x, t ) dx
O(t ) *n ( x, t )O
n
R

U
(t ) ( x,0) O
(t ) ( x,0)

U
dx
n
n

e
R

t
iH

e
n ( x,0) O

*n ( x,0)e
R

( x,0) e

*
n

t
iH

O
e

t
iH

e
O

t
iH

t
iH

t
iH

n ( x,0)
dx

n ( x,0)
dx

n ( x,0)dx

Expectation Values Revisited

O(t ) *n ( x,0) e

t
iH

t
iH

e
O

n ( x,0)dx

(t ) ( x) (0) dx
n* ( x) * (0)O
n
R

(t ) ( x)dx
( x)O
n
*
n

t
iH

h

(t ) e
where O

e
O

t
iH

(t ) ??
1 (t )OU
U

Expectation Values Revisited

e
U (t )O
1

t
iH

] 0 OH
HO
,O

If [H

2 OHH

OH

HOH

t
1 iH

O
h
k k !

H
2O
HHO

1 it

kO
H
h
k k !

Repeat k-1 times

k H

kO
OH

1 it
k
OH
h
k k !
k

1 it

e
k O
O H
h
k k !

t
iH

h

1 (t )
OU

Expectation Values Revisited

OU
1 (t )
1 (t )O
U
0
1 (t ), O
U

(t ) U
(t )
1 (t )OU
O
1 (t )U

(t ) O
OU

]0
,O
Therefore if [ H
(t ) ( x)dx
O(t ) ( x)O
n
*
n

( x)dx= O

n* ( x)O
n
R

Non Stationary States

If [H , O ] 0

(t ) U
(t )
1 (t )OU
O
cos(t ) P cos(t )
O

Which means that the observable is time dependent.

Consider that an additional interaction is introduced modifying the
Hamiltonian:

' H
O
H

where

0
,O
H

Non Stationary States

The states under this new Hamiltonian are

n (t )

n (r, t )

The Energy Levels become time dependent

n (r, t ) an (t ) n (r, t )
n

The state can change quantum number with time under the influence of
a non-commuting operator.
Non-stationary states!!!
The act of measurement can cause the system to change state
Indeterminacy??
A non-commuting operator can therefore induce the state to change
over time. (i.e the state can be influenced externally!!!)