Lecture 4

CHEM 209
Introductory Spectroscopy & Structure
Wave Mechanics

Dr. W. S. Hopkins
21st September, 2015

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Visit the discussion board for useful info about CHEM 209

2. Assignment #1 Due Date Changed

Now due 2nd October, 2015

Notable Quote:
The good thing about science is that it is true
whether or not you believe in it.
- Neil
deGrasse Tyson

Lecture 3 Recap
The Quantum Theory of Matter
Can exactly describe energy levels of single electron systems
(Bohr Theory)
The wave-particle duality of matter
Wave nature of matter can be described by a mathematical
wave function
The characteristics of wave functions lead to quantization.
x

3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5

(x)

1.0
0.5
0.0

-0.5
-1.0

| (x)|

1.0

0.5

0.0
3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5

2 | Slide

Lecture 4 Outlook
Wave Mechanics
Properties of P. E. wells (1D) Hydrogenic atoms (3D)
E proportional to (1/mL2)
Radial & Spherical Contributions
Zero-Point Energy
Quant. #s n, l & ml (magnetic
Particle-on-a-ring (2D)
projection)
Particle-in-a-box with L=r
Radial vs. Angular nodes (nodal
Introduces Ang. Momn, l
No explicit
surfaces)
No Zero-Point Energy
energy
Multi-electron systems
expression!

nuclear
charge,
Z
n=
l=

Electron correlation
4
4
Shielding
X
n=
3

l=
3

n=
2
n=
1

l=
2
l=
1
l=
0

3 | Slide

Quantum Mechanics Arrives!

Wave Mechanics (y.1926)
Matrix Mechanics (y.1925)
Concerned with wave character
Differential equation based
Relatively simple calculus

Erwin Schrdinger

Better
for
beginne
rs!

Best left
a year
or so!
Concerned with particle character

Matrix algebra based

Sophisticated transcendental algebra
Werner Heisenberg

The more I ponder about the physical part of Schrdingers

theory, the more disgusting it appears to me.
Werner Heisenberg
in a letter to Wolfgang Pauli

I was discouraged, if not repelled, by what appears to me a

rather difficult method of transcendental algebra, defying
(intuitive) visualization.
Erwin Schrdinger regarding Heisenbergs
matrix mechanics formulation

4 | Slide

Wave Mechanics
Tenets of Wave Mechanics

de Broglies matter waves are described by a mathematical wave func

Particles can only exist in certain quantized states ( la Bohr model).
Discrete states arise when electron waves constructively interfere.

Erwin Schrdinger

Illustrative Examples

Particle-in-a-box
(e.g., vibration)

No rigorous derivation
Model based on classical wave theory
Constructive interference;
produces standing wave

Particle-on-a-ring
Spherical System
Destructive
interference;
(e.g., rotation)
(e.g.,
atomic orbitals)
propagation results in

5 | Slide

Aside

Erwin Schrdinger
Magdalen College, Oxford University
1933

6 | Slide

The Rules of Wave Mechanics

1. For every molecular system there exists a wave
function,
,
contains all the information we can possibly know
about the system

2. is the solution of Schrdingers differential equation

for the system
it depends on all spatial coordinates (x,y,z) of all
particles

continuous
of
all

4. The
probability
of
a
particular
configuration is proportional to ||2

1.0

(x)

3. is a single-valued,
mathematical
function
coordinates

3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5

0.5
0.0

-0.5
-1.0

must be
somewhere

dx 1

| (x)|

normalization
condition:
every particle

1.0

0.5

0.0
3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5

7 | Slide

Top Hat Question

Top Hat Question 1

Which of the following functions is a possible wave
function?

None

All
8 | Slide

Schrdingers Equation (in 1D)

H E

A particle of mass m with total energy E

moving along the x coordinate subject to a
potential energy field V(x)

An operator is a function that

acts on a physical state to
obtain another physical state
and some relevant information

HHamiltonian Operator
Wave function
E Total Energy
xmultiplication by x

yields
position
along x-axis

William Hamilton

d
( x) E
H

2
2m dx

Kinetic
Energy

Potential
Energy

Total
Energy

Challenge:
Teach yourself more
about operators and
derive the kinetic
energy
Hint:term
p=mv
9 | Slide

Particle-in-a-Box (1D)
0

V ( x) ( x) E ( x)

2
V(x) =
2m dx

d 2 ( x) 2mE
2 ( x)
2
dx

d 2 ( x)
2

k
( x)
2
dx
Where k2 = 2mE/ is a
constant.

V(x) = 0
V(x) =

(x)

sin(kx)

cos(kx)

d(x)/dx

kcos(kx)

-ksin(kx)

d2(x)/dx2

-k2sin(kx)

-k2cos(kx)

General
Solution:

( x) A sin( kx) B cos( kx)

10 | Slide

How Does Quantization Arise?

( x) A sin( kx) B cos( kx)

1. From rule #4, for x < 0 & x > L,

( x) 0

V(x) = 0
V(x) =

V(x) =

2. Therefore, from rule #3,

( x 0) ( x L ) 0
3. Thus,

( x 0) A sin( k 0) B cos( k 0) 0

Non-trivial solutions (standing waves):

4. So,B 0
5. And, ( x L) A sin( kL) 0

2mE n
, where n = 1, 2, 3,
2

Solutions: A 0
kL n,where n = 0, 1, 2, 3,

2 2 2
n
E
2
2m L

Note: If A= 0 or n = 0, (x) =0 everywhere (trivial!)

11 | Slide

Examples 1
1. Calculate the first four energy levels for a particle of mass m
= 1 kg trapped in a box of length L = 1 m.

E
2
2
m
L

Sketch the energy level diagram.

n 2

Calculate the lowest energy

transition.

12 | Slide

The Square-well Potential

2
n=4 16Cu

2
mL

nx
( x) A sin

Energy

Normalization (for completeness)

2
n=3 9Cu
mL2

4 5

( x) dx 1
2

nx
dx 1
L

n=2 4Cu 2
mL

n=1

L
A 1
2

0 1 2 3

Cu
2
mL

~
1
n
En (cm ) Cu
2
mL

Where Cu = 16.857629056 amucm-12

A sin 2

( x)

2
L

2 nx
sin

L L
12 | Slide

What We Learn From Squarewells

Energies are
discrete &
quantized
When
L
increases:

or

~
1
n
En (cm ) Cu
2
mL

levels shift to lower

(correspondence
energies
principal)

For the nth energy

wavefunction has:
1
3
2
n
extrema

level,

the
1

3
2

(n-1) internal
nodes

13 | Slide

What We Learn From Squarewells

Energies are
discrete &
quantized
When
L
increases:

or

~
1
n
En (cm ) Cu
2
mL

levels shift to lower

(correspondence
energies
principal)

These properties apply to:

orbital motions of electron in
atoms

rotational
motion
of
molecules
radial motion of electrons in
atoms

2 d 2 ( )

E ( )
2mr 2 dr 2

2 d 2

V
(
r
)

(r ) E (r )
2
2
2mr dr

13 | Slide

Top Hat Question

Top Hat Question 2

Lets play name that
wavefunction!!!

A. 2
B. 3
C. 4

D. 5
E. 6
14 | Slide

Lord of the Ring (Wavefunctions)

Schrdinger Equation

2 d 2 ( )

E ( )
2
2
2mr d

Positive values = outside the ring

Negative values = inside the ring

Particle-on-a-Ring Wavefunctio

l ( )

1
sin( l )
2

15 | Slide

Energy Level Structure

Comparison
Particle-in-a-box
Particle-on-a-ring
n=4

l=4

n=3

l=3

n=2

l=2

n=1

l=1
l=0

2 2
~
1
n
En (cm ) Cu
2
mL

~
Cu 2
1
El (cm )
l
2
mr
16 | Slide

Top Hat Question

Top Hat Question 3

Lets play name that
wavefunction!!!

A. 2
B. 3
C. 4

D. 5
E. 6
17 | Slide

Wave Mechanics For Hydrogenic

Atoms
Schrdinger Equation

2
2

V
(
r
)

n ,l ,m ( r , , ) E n ,l ,m (r , , )
2
2 r

Easier to use spherical polar coordinates because: Quantum

Number

n ,l ,m (r , , ) Rn ,l (r )Yl ,m ( , )
Radial
Wavefunctio
ns

Spherical
Harmonic
s

Allowed
Values

Principal, n

n = 1, 2, 3,

Orbital Angular
Momentum, l

l = 0, 1, 2,
n-1

Orbital Angular
Momentum
Projection
(magnetic), ml

ml = -l, -l+1,
+l
A polar bear is merely a Cartesian bear following a coordinate transformation!
- some jacka
18 | Slide

Hydrogenic Atom Wavefunctions

n ,l ,m (r , , ) Rn ,l (r )Yl ,m ( , )
Radial Wavefunctions
n

Orbita
l

Spherical Harmonics

Rn,l(r)

1 0

1s

(Z/a)3/22e-/2

2 0

2s

(Z/a)3/2 (1/8)1/2 (2-)e-/2

2p

(Z/a)3/2 (1/24)1/2 e-/2

3 0

3s

(Z/a)
e-/2

3p

(Z/a)3/2 (1/486)1/2 (4-) e-/2

2
4
3/2 (1/2430
(Z/a)
)1/20 2 e-/2
3d 2 Z

na

( /243)

3/2 1

1/2

ml

Yl,ml(,)

1/21/2

()(3/)1/2 cos

- ()(3/2)1/2 sin ei
1+

(6-6+ )
2

e 2

For an infinitely heavy nucleus:

me & a a0, the Bohr radius

(1/4)(5/)1/2 (2 cos2 1)

- ()(15/2)1/2 cos sin ei

1+
2
3

(1/4)(15/2)1/2 sin2 e2i

(1/4)(7/)1/2 (2 5sin2 ) cos

+
(1/8)(21/)1/2 (5cos2 - 1) sin

ei

- (1/ )(105/2)1/2 cos sin2

+
4

2
3

e2i
(1/8)(35/)1/2 sin3 e3i

19 | Slide

Hydrogenic Radial Wavefunctions

I.E.

The principal quantum number, n, determines:

Orbital energies

1
~
2 A

En Z
RH 2

n
H

Mean radii

3n 2
r
a0
2Z
20 | Slide

Spherical Harmonics
YZ Plane

Orbital angular momentum

quantum number, l, defines:
Magnitude of angular momentum

l l l 1

12

Magnetic quantum number, ml,

Projection
defines: of l onto the z-axis

1 e- angular
wavefunctions (orbital
shapes)

l z ml
21 | Slide

Orbital Density Plots (YZ Plane)

n ,l ,m (r , , ) Rn ,l (r )Yl ,m ( , )
X

1s

nl

ml

Orbita
ls

1 0

1s

2 0

2s

3 0

3s

= [# radial nodes] + [# angular

nodes]
+
2 1 0,1
2p
3 1 0,1

l = # angular nodes
3 2 0,1,
2s

2pz

2py

3s

3pz

3py

3p
3d

2 a p and
Arent we missing
two d orbitals from these
density plots? Why?

3dz

3dyz

3dx -y
2

22 | Slide

An Orbital Picture of the Periodic

Table

23 | Slide