Lecture # 8

Quantum
Theory and the
Electronic
Structure of
Atoms and
molecules

QUANTUM MECHANICS

Failure of classical mechanics

1. Black body radiation: Planck

2. Heat capacities: Einstein

3. Photoelectric effect: Einstein Photon is a

particle of light

4. Line Spectra: Bohr

Black-body radiation

Energy (light) is emitted or absorbed in

discrete units (quantum).

Planck
1900

E =n x h x
Plancks constant (h)
h = 6.63 x 10-34 Js
n = 1, 2, 3, (integer)

Line Emission Spectrum of Hydrogen Atoms

Bohrs Model of the Atom (1913)

1. e- can only have specific

(quantized) energy values
2. light is emitted as e- moves from
one energy level to a lower energy
level

En = -RH (

1
n2

n (principal quantum number) = 1,2,3,

RH (Rydberg constant) = 2.18 x 10-18J

Balmer Series Limit

For n

1
~
109680( 0)cm 1 2.742 10 4 cm 1
4

Balmer Series limit

Emission Energy
ni = 3

ni = 3

ni = 2
nf = 2

nnf f==11

E = Ef - Ei
1
Ef = -RH ( 2
nf
1
Ei = -RH ( 2
ni
1
E = RH( 2
ni

)
)
1
n2f

Max
Quantum Theory:
Planck
Atoms and molecules
absorb and emit energy in discrete
quantities quanta -

E = h

The deBroglie Duality of Matter

E= mc2

(Einstein);E=h (Planck)

Photonmomentum

h
p=
;
c

p=

h
,

P =mv =mc

c
,

h
=
mv

2 r n
Mvr =
nh

nh
v
mr

Prince
Louis deBroglie

An integral multiple of
wavelengths must fit
in the length 2r,
otherwise destructive
interference would
occur.

Circumference2r=n

Davisson-Germer Experiment

Davisson-Germer Experiment

Diffraction Pattern from Aluminum

X-ray diffraction

Electron diffraction

Quantum Mechanics

Heisenberguncertaintyprinciple:
Theexactpositionandvelocitycannotbe
measuredsimultaneously,onlywithinh/4.

h
xp
4
h

xmv

4 2

h
(
)
2

Schrodinger Wave Equation

In 1926 Schrodinger wrote an equation that described both
the particle and wave nature of the eWave function () describes:
1 .energy of e- with a given
2 . probability of finding e- in a volume of space
Schrodingers equation can only be solved exactly for the
hydrogen atom. Must approximate its solution for multielectron systems.

Schrodinger Equation

u 1 u
2 2 Classical
2
x t
2

1D wave eqn: u(x,t)= amplitude;v = sped

u(x, t) (x, t)cos t (x)

d
2 (x) 0
2
dx
2

p2
E
U(x)
2m
E (total KE

PE

is a spatial wave
amplitude

p [2m( E U ( x))]1/ 2

h
h

p [2m(E U(x))]1/2

v
2 4 2 2 4 2 [2m( E U ( x))]

2
2
2
v
v

h2

d 2m

[E
U(x)]

(x)

0
2
2
dx
h
2

Schrodinger equation

2 d 2
U ( x ) ( x ) E ( x )

2
2m dx

Schrodinger equation

Hamiltonian
operator

H (x) E (x)

3.8

d 2mE
2 ( x) 0 0 x a
2
dx

A (x) a (x)

(x) eigenfunction

a eigenvalue

2
2 d 2
p2
K

2
2m dx
2m
2
d
d
22

2
p
i
2
dx
dx

K = KE

d
i
dx

d 2 2mE
2 ( x) 0 0 x a
2
dx

( x) A cos kx B sin kx

Solution

(2mE )1/ 2
k

Particle in box ( confined electron)

if (0) 0 then A 0

(a ) B sin ka 0

B 0, ( x) 0 for all x
For

ka n , n 1,2,...

h2n2
En
n 1,2,.
2
8ma

n ( x) B sin kx
B sin

nx
a

n 1,2,3.....