量子物理講義

清大遠距課程
量子物理講義

目錄

Ch2 ....................................................................................................................................... 1

Ch3 ..................................................................................................................................... 24

Ch4 ..................................................................................................................................... 44

Ch5 ..................................................................................................................................... 68

Ch6 ..................................................................................................................................... 98

Ch7 ................................................................................................................................... 124

Ch8 ................................................................................................................................... 143

Ch9 ................................................................................................................................... 167

Ch2 Particle
properties of
waves

1
Chapter 2 Particle properties of waves

Electronics: particles charge , mass Wave?

Electromagnetic wave: wave diffraction, interference,

Polarization particle?

Wave-particle Duality

2.1Emwaves

Changing magnetic field current (or voltage)

Maxwell proposed: changing electric field magnetic field

Hertz created EM waves and determined the wavelength and

speed of the wave, and showed that they both have E and B

component, and that they could be reflected, refracted, and

diffracted. Wave characteristic.

2
Principle of Superposition:

When two or more waves of the same nature travel past a point

at the same time, the instantaneous amplitude is the sum of the

instantaneous amplitude of the individual waves.

3
Constructive interference same phase, greater amplitude

Destructive interference different phase, partial or

completely cancellation of waves

Interference wave characteristic

Young’s diffraction experiments:

diffraction wave characteristic

4
2.2Blackbody radiation

Is light only consistent of waves? Amiss: understand the origin

of the radiation emitted by bodies of matter.

Blackbody: a body that absorbs all radiation incident upon it,

regardless of frequency.

A blackbody radiates more when it is hot than it is cold, and the

spectrum of a hot blackbody has its peak at a higher frequency

than that of a cooler one.

5
Considering the radiation inside a cavity of absolute temperature

T whose walls are perfect reflectors to be a series standing EM

waves.
L  n* / 2

Density of standing waves in cavity

G( )d  8 2d / c3

The higher ν, the shorter the wavelength, and the greater the

number of possible standing waves.

The average energy per degree of freedom of an entity that is a

member of a system of such entities in thermal equilibrium at T

is 1/2kT. K is Boltzmann’s constant=1.381*10-23J/k

6
An idea gas molecular has three degree of freedom: kinetic

energy in three independent directions 3/2kT

One dimensional harmonic oscillator has two degree of freedom:

kinetic energy and potential energy.

Each standing wave in a cavity originates in an oscillating

electric charge in the cavity wall. Two degree of freedom.

Classic average energy per standing wave   kT

Total energy per unit volume in the cavity in  and  +d

u ( )d  G( )d  (8kT / c3 ) 2d Rayleigh-Jeans formula

2
 increase energy density increase with  .

In the limit of infinitely high frequencies, u(  )d  goes to

infinity. In reality, the energy density(and the radiation rate)falls

to 0 as  goes to infinity. Ultraviolet catastrophe

7
Plank Radiation Formula

u( )d =(8πh/c3)( 3d )/(eh /kT-1)

h is planck’s constant=6.626*10-34Js

h >>kT eh /kT 

u( ) 0

No ultraviolet catastrophe.

In general, ex=1+x+x2/2+………

When h << kT, 1/(eh /kT-1)~1/((1+(h /kT)-1)~kT/h

u( )d ~(8πh/c3)( 3d )/( kT/h )~(8πkT/c3) 2d

which is Rayleigh-Jeans formula.

8
How to justify the Plank radiation formula

The oscillators in the cavity walls could not have a continuous

Distribution of possible energy ε but must have only specific

energies εn=nh n=0,1,2……

An ocillator emits radiation of frequency  when it drops from

one energy state to the next lower one, and it jumpsto the next

higher state when it absorbs radiation of . Each discrete bundle

of energy h is called a quantum.

With oscillator energies limited to nh  , the average energy per

oscillator in the cavity walls turn out to be not kT as for a

continuous distribution of oscillator energies, but

ε=h /(eh /kT-1) average energy per standing wave

9
2.3 Photoelectric effect

Some of photoelectrons that emerge from the metal surface have

enough energy to reach the cathode despite its negative polarity

Current

When V is increased to a certain value V0, no more

photoelectrons arrive. V0 correspond to the max photoelectron

kinetic energy.

Three experimental finding:

(1)No delay between the arrival of the light at the metal surface

and the emission of photoelectrons.

(2) A bright light yields more photoelectrons than a dim one,

but highest electron energy remain the same.

10
(3)The higher the frequency of the light, the more energy the

photoelectrons have. At the frequencies smaller than  0,

which is a characteristic of the specific metal, no more

electrons are emitted.

Quantum theory of light

Einstein proposed Photons. The energy in light is not spread out,

but is concentrated in small packets. Each photon of light of

frequency  has the energy h .

Einstein proposed that energy was not only given to em waves

in separate quanta but was also carried by the waves in separate

quanta.

10

11
Explanation of experiments:

(1)Since em wave energy is concentrated in photons and not

spread out, there should be no delay in the emission.

(2)All photons of frequency  have the same energy h  .

Changing the intensity of light only change the number of

photoelectrons but not their energy.

(3)The higher , the greater photon energy and so the more

energy the photoelectrons have.

νo corresponds to the min energy Φ for the electron to escape

from the metal surface. This energy is called work function.

Φ=hνo

Photoelectric effect hν=kEmax+Φ

h = kEmax+hνo

kEmax=h(ν-νo).

Photo energy

E=(6.626*10-34Js/1.602*10-19J/eV )ν=(4.136*10-15)νeVs

ν=c/λ E=1.24*10-6eVm/λ

11

12
 What is light

Wave model: light intensity  E2

Particle model: light intensity  N(#of photons/sec.area)

N  E2

.N is large interference pattern

N is small a series of random flashes

.if keep track of flashes for long time

same as large N

intensity of wave at a given place on the specific space

 the probability of finding photons.

12

13
Wave & quantum theory complement each other.

photoelectric effect : Ephotons Ee΄

yes x-ray

faster e΄ more x-ray

# of e΄ increase Intensity of x-ray increase

.for given accelerating V λ min

V λ min

.most of e΄ heat

A few e΄ lose E in single collisions x-ray

13

14
 .x-ray are em waves

EM theory predicts that an accelerated electric charge will

radiate em waves, and a rapidly moving e΄ suddenly brought to

rest is certainly accelerated Bremsstranlung (“braking

radiation”)

x-ray at specific λ nonclassical

* different targets give different characteristic x-ray

* for the same V, λmin is the same for different materials

λmin=(1.24  10-6)/V(m)
14

15
hνmax = Ve = hc/λmin λmin = hc/Ve = (1.24  10-6)/V

Scattering by an atom (wave model)

atom in E polarized distorted charge distribution

electric dipole

em wave with ν on atom polarization charge with ν

oscillating electric dipole radiate em wave

x-ray falls on a crystal will be scattered in all directions because

of regular arrangement of atoms constructively interference

Bragg’s condition (2dsinθ=λ)

15

16
 Compton effect

Loss in photon energy=gain in e΄ energy

hν -hν΄ =kE

for massless particle E= Pc (P=momentum)

photon momentum P =E/c = hν/c

16

17
hν/c = (hν΄/c)cosΦ+ Pcosθ (parallel)……..(1)

0 = (hν΄/c)sinΦ – Psinθ () ……………….(2)

(1)&(2)x c

Pc(cosθ) = hν -hν΄cosΦ

Pc(sinθ) = (hν΄)sinΦ

P2c2 = (hν)2 – 2(hν)(hν΄)cosΦ +(hν΄)2

17

18
& E = KE + moc2 E= mo c 4  P 2c 2
2

(KE + moc2)2 = mo2c4 + P2c2

P2c2 = KE2 + 2moc2KE

Because KE = hν - hν΄

P2c2 = (hν - hν΄)2 + 2moc2KE

2moc2(hν - hν΄) = 2(hν)(hν΄) (1 –cosΦ)……(3)

(3)/2h2c2 moc/h(ν/c - ν΄/c) =(ν/c)( ν΄/c)(1 –cosΦ)

moc/h(1/λ – 1/λ΄) =(1 –cosΦ)/( λλ΄)

λ΄ - λ = (h/moc)(1 –cosΦ) = λc(1 –cosΦ)

λ=Compton wavelength

18

19
 Relativistic formulas
mo c 2
Total energy E= mo= rest mass
v2
1 2
c
mo v
Relativistic momentum P = 2
1 v
c2

When mo = 0 (massless particle) & v<c E=P=0

How about v=c , mo= 0 E=0/0 , P=0/0 (any values)

2 2 2
mo c 4 mo v 2 mo v 2 2
E2 = 2
, P2= P2c2 = c
1 v 2 v2 v2
c 1 2 1 2
c c
2
mo c 4
E –P c
2 2 2
= 2 (1-v2/c2) = mo2c4
1 v 2
c

E2 = mo2c4 +P2c2

m0 c 4  p 2c 2 Eo  p 2c 2
2 2
For all particles E= =

Restriction of massless particles : E = Pc (mo=0)

2 2 mo c 2
Total energy mc =moc +KE = 2
1 v
c2

19

20
 Pair production

A photon give an e΄ all of its energy photoelectric

part of its energy compton

a photon materialize into an e΄ & position

20

21
(momentum is conserved with the help of the nucleus which

carries away enough photon momentum)

rest energy moc2 of electron or position is 0.51Mev pair

production requires a photon energy  1.02Mev

 pair production cannot occur in empty space

concervation of energy hν = 2mc2

momentum concervation hν/c = 2Pcosθ hν = 2Pc(cosθ)

P = mv hν = 2mc2(v/c) cosθ

v/c <1 & cosθ  1 hν < 2mc2

21

22
linear attenuation coefficient
 dI
 udx I = Ioexp(-ux)
I
Io
ln( )
absolute thickness x= I
u

22

23
Ch3 Wave
properties of
particles

24
 CH3 Wave Properties of Particles

.De Broglie waves

A moving body behaves in certain ways as though it has a wave

nature.

* for photon

P = hν/c =h/λ

Photon wavelength λ= h/P………(3.1)

De Broglie Suggested (3.1) is general one that applies to

material particles as well as to photons.

De Broglie wavelength

λ= h/P = h/mv
mo
(m = )
2
1 v
c2

25
Example 3.1

Find the de Brogli wavelengths of

(a) 46-g golf ball with a v = 30 m/s

(b) e’ with a v = 107m/s

(1) v<<c m =mo

λ= h/mv =6.63x10-34Js/(0.046kg)(30m/s)=4.8x10-34m

wavelength is very small

λ= h/mv =6.63x10-34Js/(9.1x10-31kg)(107m/s)=7.3x10-11m

=0.73Å

the radius of H atom = 5.3x10-11m=0.53 Å

wave character of moving e’ is the key to understand atomic

structure behavior

26
3.2 Waves of probability

Water wave (varing quantity) height of water surface

Light wave E& H fields

How about matter waves

Wave function Ψ

The value of wave function associated with a moving body at

the particular point x , y, z at time t is related to the likehood

of finding the body there at the time.

*Ψ has no direct physical significance

0  probability  1

but the amplitude of wave am be positive or negative

no negative probability


2
:squae of the absolute value of wave function

probability density

** The probability of experimentally finding the body described

by the wave functionΨat the point x , y , z at time t is


2
proportional to there at t.

wave functionΨthat described a particle is spread out is spall,

but it does not mean that the particle itself is spread out.

27
3.3 Describing a wave

de Broglie wave velocity vp

vp =νλ(λ=h/mv)
2 2
hν=mc ν=mc /h

De Broglie phase velocity vp = νλ=(mc2/h)(h/mv)=c2/v (v =

particle velocity)

Because V<C

de Broglie waves always travel faster than light !!

Phase velocity, group velocity.

28
At x=0, y=Acos(2  t) for time=t

x = vpt , t =x/vp

y=Acos2  (t  x / v p )

the amplitude for y(x,t) = y(0,t-x/vp)

y = Acos2  (vt  vx ) vp = νλ
vp

y =Acos2  (vt  x /  )

angular freguency ω= 2πν wave number k= 2π/λ=ω/vp

y = Acos(ωt – kx)

29
The amplitude of de Broglie waves probability

De Broglie wave can not be represented by y=Acos(wt-kx)

. wave representation of a moving body wave packet

wave group

. An example is a beat. (two sound waves of the same amplitude

but slightly different frequencies)

original 440, 442 Hz hear fluctuating sound of 441 Hz with

2 beats/s

a wave group: superposition of individual waves of different λ

which interference with one another

variation in amplitude define the group shape

30
(1) If the velocities of the waves are the same the velocity

of wave group is common phase velocity

(1)If the phase velocity varies with λ

an effect called dispertion

individual waves do not proceed together

wave group has a velocity different from the phase

velocities

the case of de Broglie wave

 group velocity

y1 = Acos[(ωt –ks)]

y2 = Acos[(ω+Δω)t – (k+Δk)x]

y =y1+y2 =2Acos1/2[(2ω+Δω)t –(2k+Δk)x]cos1/2(Δωt-

Δkx)

because Δω<< ω 2ω+Δω  2ω

Δk << k 2k+Δk  2k

Y = 2Acos(ωt –kx)cos[(Δω/2)t – (Δk/2)x]

A wave of angular frequency ω & wave number k that has

superimposed upon it a modulation of angular frequency 1/2Δω

& of wave number 1/2Δk

31
Modulation produce wave group

 2
vp = 
2
  phase velocity
k


vg =Δω/Δk = dω/dk group velocity

for de Broglie waves

2 mc2 2mo c 2
  2   (because hν=mc2)
h 2
h 1 v 2
c
2 2m 2mo v
k   (because λ=h/mv)
 h h 1 v
2

c2
d
* both ω&k are functions of body’s v vg = dω/dk = dk dv
dv
d 2mo v
 dk 2mo
  , 
2

 
dv 2 3
h1 v 3 dv 2
c2
h1 v 2
c2

vg = v (de Broglie group velocity)

De Broglie wave group associated with a moving body travels

with the same velocity as the body.

De Broglie phase velocity vp =ω/k=c2/v

vp > velocity of the body v > c

(∵ it is not the motion of the body)

32
Ex 3.3 :
-12
An e' has a de Broglie wavelength of 2pm=2x10 m.Find its kinetic

energy & the phase & group velocity of its de Broglie waves.

(a) E =Eo+kE kE =E – Eo= Eo  p 2c 2  Eo

2

-15 8 -12
pc = hc/λ= (4.136x10 ev.s)(3x10 m/s)/(2x10 ) =
5
6.2x10 ev=620kv

the rest energy of e' is Eo=511kv

kE= 5112  6202  511  292 kev

(b) e' velocity

2
Eo Eo
E v  c 1  0.771c
2 E2
1 v
c2

∴ vp = c2/v =1.3c , vg = v = 0.771c

33
3.5 particle diffraction e'-beam diffraction

confirm de Broglie waves

The method of plotting is such that the intensity at any angle is

propotional to the distance of the curve at the angle from the

point of scattering.

nλ=2dsinθ λ=2dsinθ=0.165nm λ=h/mv=0.166nm

10

34
11

35
3.6 particle in a box

a prticle trapped in a box = a standing wave.

Ψmust be zero at the walls

λn =2L/n n=1,2,3……

De Broglie wavelength of trapped particles.

2 2 2 2
KE=1/2(mv )=(mv) /2m=h /(λ 2m)

∵λn=2L/n KE+v=En the energy for the

particle in a box

En=n2h2/8mL2 n=1,2,3……..

Each permitted energy is called an energy

level.(n=quantum number)

This can be applied to any particle confined

to a certain region of space.

For example

e-

nucleus

12

36
 1. Atraped particle cannot have an arbitrary energy, as a free

particle can .

Confinement leads to restriction on its wave function that alloy

the particle to have certain energies.

2. A trapped particle cannot have zero energy.

∵ de Broglie wavelength λ=h/mv If v =0 λ=∞

it can not be a trapped particle.

-34
3. ∵ h =6.63x10 Js very small

∴ only if m & L are very small, or we are not aware of energy

quantization in our own experience.

Ex 3.4

An e' is in a box 0.1nm across, which is the order of magnitude of

atomic distance, find its permitted energy.

-31 -10
m=9.1x10 kg & L=0.1nm=10 m
2 -34 -31 -10 2 -18 2 2
En=n (6.63x10 )/8x(9.1x10 )(10 ) =6x10 n J=38n ev

When n=1 38 ev

n=2 152ev see fig 3.11

n=3 342 ev

13

37
Ex 3.5

A long marble is in a box 10 cm across, find its permitted energies

-64 2 -64 -31
En = 5.5x10 n J n=1 E=5.5x10 J v=3.3x10 m/s

Which can not be experimentally distinguished from a stationary

marble.
30
For a reasonable speed 1/3 m/s n=10 !!

Energy levels are very close quantum effects are imperceptible

 Uncertainty principle

* wave group narrower particles

position precise.

However, λof waves in a narrow packet is

not well defined ∵λ=h/mv ∴ P is not

precise

* A wide wave group clearly definedλ

but position is not certain

14

38
uncertainty principle:

It is impossible to know both the exact position & exact momentum

of an object at the same time.

An infinite # of wave trains with different frequencies wave

numbers and amplitude is required for an isolated group of arbitrary

shape.

 x    g k cos kxdk Fourier integral
0

g(k): amplitude of the waves varying with k , furrier transform

of φ(x)

15

39
* wave numbers needed to represent a wave group extend from

k=0 to k=∞, but for a group which length Δx is finite

waves which amplitudes g(k) are appreciable have wave number

that lie within a finite interval Δk the shorter the group,

the broader the range of wave numbers needed.


 x  xo  2
1 2 2
*Gaussian function: f(x)= e
 2

1 n
Standard deviation    xi  xo 2 (square-root-mean)
n i 1

Width of a gaussian curve at half its max is 2.35σ

x o 

p x o    f x dx  0.683
x o 

16

40
 Min ΔxΔk occur for Gaussian function

Take Δx,Δk as standard deviation ofφ(x)& g(x) ΔxΔk=1/2

∴ in general ΔxΔk  1/2

∵ k=2π/λ = 2πP/h P=hk/2π ΔP =hΔk/2π

∵ΔxΔk  1/2 Δk  1/2Δx

ΔxΔp  h/4π (∵Δx(hΔk/2π)  h/4π)


ΔxΔp  [  =h/2π]
2

Ex 3.6

A measurement establishes the position of a proton with an

accuracy of ± 1.00x10-11m. Find the uncertainty in the proton’s

position 1.00s later. Assume v<<c

Sol: At time t=o, uncertainty in positionΔxo= 1.00x10-11m


The uncertainty in P at this time 
2xo

∵ΔP =moΔv Δv =ΔP/mo 
2mo xo
t 3
Δx =tΔv  =3.15x10 m (∵Δx α 1/Δxo)
2mo xo

*the more we know at t=0, the less we know at t=t *

17

41
look at e' light of wavelengthλ P=h/λ when one

of three photons bounces off the e' e' momentum is changed.

The exact P cannot be predicted, but ΔP~h/λ (the order of

magnitude as P) Δx~λ

ie if we use shorterλ increase accuracy of position

higher photon momentum disturb e' motion more

accuracy of the momentum measurement deceasing

ΔxΔP≧ h (consist with ΔxΔP≧  /2)

(1) If the energy is in the form of em waves, the limited time

available restricts the accuracy with which we can determine the

frequencyν.

(2) Assume the min uncertainty in the number of waves we count in

a wave group is one wave.

18

42
∵Frequency of wave = # of wave/time interval Δν≧ 1/Δt

∵E=hΔν ΔE≧ h/Δt or ΔEΔt≧ h

more precise calculation ΔEΔt≧  /2

ex 3.9

An “excited” atom gives up its excess energy by emitting a photon

of characteristic frequency. The average period that elapses between

-9
the excitation of an atom & the time it radiates is 1.0x10 s. find the

uncertainty in the frequency of the photon.

-27
ΔE≧  /2Δt=5.3x10 J
6
Δν=ΔE/h = 8x10 Hz

19

43
Ch4 Atomic
structure

44
 Chapter 4. Atomic structure
Thomson model of the atom

Geiger and Marsden’s experiment:

According to Thomson model, it was expected that the alpha

particle (helium atoms lost two e', leaving charge of +2e) would

go right through the foil with hardly any deflection. (Since the

electron charge inside an atom is uniformly spread out its

volume, only weak electric forces can exert on the alpha

particle)

45
Although most of the alpha particles indeed were not deviated

by much, a few were scattered through very large angles. Some

were even scattered backwards.

Rutherford model

With an atom being largely empty space, it is easy to see why

most alpha particles go right through a thin foil. However, when

an alpha particle happens to come near a nucleus, the intense E

field scatters it through a large angle. The e' is do light that they

do not appreciable affect the alpha particles.

The deflection of an alpha particle depends on magnitude of the

nuclear charge.

All the atoms of any one element turned out to have the same

unique nuclear charge, and this charge increased regularly in the

periodic table.

46
The nuclear charges turned out to be multiples of +e, the number

Z in the nuclei of an element is called atomic number of the

element.

In fact, the proton with charge +e provide the charge on a

nucleus, so the atomic number of an element is the same as the

number of protons in the nuclei of its atoms.

Rutherford scattering formula

Ni ntZ 2e 4
N   
8 o 2 r 2 KE 2 s i 4n 2 

N(θ) number of alpha particles per unit area that reach the screen

at a scattering angle ofθ

Ni=total number of alpha particles that reach the screen

n=number of atoms per unit volume on the foil

Z=atomic number of the foil atoms

R=distance of screen from the foil

KE=kinetic energy of the alpha particles

t=foil thickness

47
Because N(θ) is inversely proportional to sin4(θ/2): only 0.14

percent of the incident alpha particles are scattered by more than

1o.

Nuclear Dimensions

Rutherford assumed that the size of a target nucleus is small

compared with the minimum distance R to witch incident alpha

particles approach the nucleus before being deflected away.

A way to find an upper limit to nuclear dimensions.

Smallest R=when alpha particles approach a nucleus head on,

which will be followed by a 180o scattering.

1 2Ze2
KE = PE = (∵ αparticle 2+e nucleus Z+e)
4 o R

R = 2Ze /(4 π ε oKE)=3.8x10-16 Z(m)

2
(for KE of α

48
particle=7.7Mev)
-14 -4
For gold . Z=79 R(Au)=3x10 m (<<10 the radius of atom)

Electron orbits

e' cannot be stationary in this model, because there is nothing

that can keep them in place against the electric force pulling

them to the nucleus the e' needs to be in motion

Assume a circular electron orbit

Fc =mv2/r (centripetal force)

1 e2
Fe= (electric force)
4 o r 2

1 e2 e
Fc = Fe mv2/r = v=
4 o r 2 4 o mr

e2
Total energy E = KE + PE =(1/2)mv2+(- )
4 o r
e2 e2
= -
8 o r 4 o r
e2
Total energy of H atom E= - (negative energy e' is
8 o r

bound to nucleus)

49
The failure of classical physics

According to EM theory, the accelerated electric charges radiate

energy in the form of em waves. An electron pursuing a curved

path is accelerated and therefore should continuously lose

energy, spiraling into the nucleus in a fraction of a second.

Classical physics fails to provide a meaningful analysis of

atomic structure because it approaches nature in terms of “pure”

particles and “ pure” waves.

The usefulness of classical physics decreases as the scale of the

phenomena under study decrease. We must use the

particle behavior of waves and the wave behavior of particles to

understand the atom. Bohr model

50
Atomic spectra

Emission line spectra

Every element displays a unique line spectrum when a sample of

it in the vapor phase is excited. Spectroscopy is useful tool for

analyzing the composition of an unknown substance.

51
Absorption line

When white light is passed through a gas, the gas is found to

absorb light of certain of the wavelength present in its emission

spectrum.

The number, strength, and wavelengths of the lines depend on

temperature, pressure, the presence of electric and magnetic

field, and the motion of the source.

Spectral series

Balmer series 1/λ=R(1/22 –1/n2) n=3,4,5……..

Rydberg constant R=1.097x107m-1=0.01097nm-1

52
Lyman series 1/λ=R(1/12 –1/n2) n=2,3,4…….

Pachen series 1/λ=R(1/32 –1/n2) n=4,5,6……..

Brackett series 1/λ=R(1/42 –1/n2) n=5,6,7……..

Pfund series 1/λ=R(1/52 –1/n2) n=6,7,8………

53
10

54
4.4 Bohr atom

de Broglie wavelength of e' λ=h/mv

e h 4 o r
v 
4 o rm e m

-11
let r =5.3x10-11m λ= 33x10 m

λis exactly the same as 2πr

*An electron can circle a nucleus only if its orbit contains an

integral number of de Broglie λ

nλ=2πrn n=1,2,3……..quantum number

h 4 o
n  2rn (see Fig 4.12,4.13,4.14)
e m

n 2 h 2 o
Orbital radii in Bohr atom r n= n=1,2,3…..
me2

When n=1 , the radius is called Bohr radius ao

ao =5.292x10-11m , rn= n2ao

11

55
4.5 energy level and spectron

En=  me  1  E1
4
e2
∵ En= 2 2  2 
 2
8 o rn 8 o h  n  n

E1=-13.6ev(see fig 4.15)

These levels are all “-“, which signifies that the e' does not have

enough energy to escape from the nucleus.

E1 : ground state

E2,E3,E4……: excited state

 The work needed to remove an electron from an atom in its

ground state is called its ionization energy.The ionization

energy = - E1

When an electron in an excited state drops to a lower state, the

lost energy is emitted as a lingle of light.

Ei - Ef = hν
2 2 2 2
E1 (1/ni – 1/nf ) = -E1(1/nf -1/ni ) =hν
2 2
ν= -E1/h(1/nf -1/ni )
2 2
1/λ= (-E1/ch)(1/nf -1/ni ) (see fig 4.16)
4
the constant E1
= me3 3  1.097  107 m1 =Rydberg constant
ch 8 o ch

12

56
4.6 Correspondence Principle

the greater the quantum number, the closer quantum

physics approaches classical physics.

According to EM theory, an e' moving in a circular orbit radiates

em waves whose ν are equal to its ν of revolution and to

harmonics(integral multiples) of that frequency.

e
In H atom, v =
4 o mr

e
Frequency of revolution f = v/2πr =
2 4 0 mr 3

n 2 h 2 o me4  2   E1  2 
∵ rn  f     
me2 8 0 h3  n3 
2
h  n3 

 From the Bohr theory

 E1  1 1 
 
h  n f 2 ni 2 

let ni = n , nf = n-P (P=1,2,3……)

 E1  1 1   E1  2np  p 2 
     
h  n  p 2 n 2  h  n 2 n  p 2 

when ni & nf are both very large n>>P

 
and 2np-p2 2nP (n-P)2 n2

 E1  2 p 
  
h  n3  same as classical em theory

13

57
4.7 Nuclear Motion

The nuclear mass effects theλof spectral lines.

Both nucleus & e' revolve around their common center of mass,

which is very close to the nucleus because nuclear mass is much

greater than that of the e' .

a single particle of mass m' revolves around the position of the

heavier particle.

Reduced Mass m'=mM/m+M

  me 1  m  E1 
4
En     
8 o h 2 n 2  m  n 2 
2

In H m'/m=0.99945

Increase of 0.055% (∵E is ”-“ )

Reduced mass deuterium

MD= 2MH (neutron + proton)

14

58
∵ mass increases spectral lines of D shifted to shorter

wavelength.

15

59
4.8 Atomic excitation

Two ways for an atom to be excited

(1) collision with another particle (KE is absorted)

excited atom ground state (10-8sec)

hν

(2)atoms absorbs a photon of light whose energy is just the right

amount to raise the atom high level

 collision

∵ energy transfer is a max when the colliding particles have

the same mass. e' is more effective than ions to provide

energy to atomic electrons.

Ex: Neon signs &mercury-vapor lamps.

16

60
Photon absorption

Hn=1 absorption Hn=2 reradiation Hn=1

hν hν radiation

The resulting excited H atoms reradiate their excitation energy

almost at once, but these photons come off in random directions,

with only a few in the same direction as the original beam of

white light The dark line in an absorption spectrum are

never completely black.

V0: prevent e’ having energies less than a certain minimum from

contributing to current I

17

61
Franck-Hertz experiment when V # of e’ I it is

not the case, at some specific V

 If KE is conserved when e’ collides with atoms in vapor,

the e’ merely bounces off in a new direction.(∵e’ is light

almost no KE loss)

 at a critical V I e’ colliding with one of atoms gives

up some or all of its KE to excite atom to higher energy level.

In elastic

 when V again I again( ∵ e’ now have enough

energy left to reach the plate after an inelastic collision)

 V another sharp drop

Excitation of the same energy level in other atoms by e’

* to check critical V is due to atomic energy level Check

emission spectra for Mercury vapor: 4.9eV was required to

excite 253.6nm spectra line.

18

62
4.9 Laser: light amplification by stimulated emission of

radiation

.coherent: in phase

.monochromatic: single λ

.very little diverge.

.intense

key for Laser: presence of meta stable states

19

63
Three kinds of transition between two energy levels.

In induced emission, the radiation waves are exactly in phase

with the incident ones enhanced beam of coherent light.

* Pinduced emission=Pinduced absorption

 three-level laser

 We want more atoms in Metastable state than in group stat .

Shine hν more induced emission than induced absorption

amplification of light.

20

64
 population inversion an assembly of atoms in which the

majority are in energy levels above ground state.

 optical pumping: external light photons raise ground-state

atoms to excited state metastable state

 if only two levels more photons upward transition

induced downward /transition half the

atoms are in each state

Rinduced emission=Rinduced absorption

No laser amplification

21

65
∵ very few atoms in intermediate modest amount of

pumping is enough to populate the metastable state to greater

than intermediate state.

 Ruby laser: Al2O3, some of Al+3 are replaced by Cr+3 xenon

flash lamp excite Cr+3 to higher energy

Fall to metastable level by losing energy to other ions

Photons from spontaneous decay of some Cr+3 are reflected

back & forth between mirrored ends of ruby rod

Stimulating other excited Cr+3

* rod’s length=(λ/2)n standing wave.

22

66
He-Ne laser: 10He/1Ne at low pressure.

.use electric discharge collisions with e’ from discharge

excite. He&Ne to metastable states

.Some of excited He transfer energy to ground state Ne in

collisions

*The purpose of He is to help achieve a population inversion in

Ne

Since the e’ impacts the excite He&Ne occur all the time

He-Ne laser operates continuously.

23

67
Ch5 Quantum
Mechanics

68
 Chapter 5 Quantum Mechanics

 limitation of Bohr theory:

1. Can not explain why certain spectral lines are more intense

than others.

2. many spectral lines actually consist of several separate lines

whose λ differ slightly.

3. an understanding of how individual atoms interact with one

another to from macroscopic matters Quantum

mechanics(1925~1926)

5.1 Quantum Mechanics

Classical mechanics future history of a particle is

completely determined by its initial position & momentum

together with force.

Quantum Mechanics suggest the nature of an observable

quantity uncertainty principle probabilities

classical mechanics is an approximate version of quantum

mechanics

Wave function φ.

 2
probability of finding the body for complex φ  2=

69
 * *
φ*φ (φ : complex conjugate)
* * 2 2
φ=A+ιB φ =A-ιB φ φ=A +B
“
 well behaved” wave function

(1)φmust be continuous & single-valued everywhere

(2)  x ,  y ,  z must be single valued & continuous(for

momentum consideration)

(3) φmust be normalization, which means thatφ must go to 0 as x

 y  z 

   dv needs to be a finite constant

2

 
2
= probability density P
 

 pdv  1   dv  1
2

 
normalization

px1 x 2    dx
2
probability
x1

 a particle in a box, φ=0 outside the box but in real case,

never happen.

70
5.2 wave equation
2 y 1 2 y
 solution: y=F(t  x/v)
 2 x v 2  2t

consider a wave equivalent of free particles.

ω
Y=Ae-i (t- x/v)
{undamped(constant amplitude A),

monochromatic( const ω), harmonic}

Y=Acosω(t – x/v)-iAsinω(t – x/v)

For a strenched string, only real part has significance.

71
5.3 Schrodinger’s equation : time dependent form
(t  x / v ) 2i (t  x
 for a free particle   Ae i  Ae 
)

h 2
 E  h  2 ,   
p p
 i ( Et  px)
   Ae h
............( A)

unrestricted particle of energy E & momentum P moving in

+x direction

(1)differentiating eq(A) for φ twice with respect to x

 2  p
 2 
x 2 
 2
p 2   2 2
x

(2) differentiating eq(A) forφwith respect to t

  iE
 
t 
  
E 
i t

for v<<c
p2
E  U ( x, t )
2m
p 2
 E   U
2m
   2  2
 i   U 
t 2m x 2
restrictio n  U

Derived from free particle, but it is a general case. If U known

φcan be solved.

72
5.4 Expectation value

calculated the expectation value <x>

 The value of x we would obtain if we measure the

positions of a great many particles described by the same

wave function at time t and then average the results.

 The average position x of a number of identical particles

distributed along x axis.

N1 at x1 , N2 at x2 ;……………

x
N1 x1  N 2 x2  N3 x3  .......

N x i i

N1  N 2  N3  ...... N i

 If along with a single particle,

 replaced Ni by probability Pi

pi   i dx
2

 x
2
dx
 x  



2
dx


If φ is a normalized function

  dx  1
2




x   x
2
dx

 Expectation value of position 
G x    G  x   dx
2



73
5.5 Schrodinger’s equation: steady-state form

for one-dimensional wave function Ψ of an unrestricted

particle may be written

   Et  px
 i   t
 iE   ip  x   t
 iE
  Ae  Ae e  
 e

  t
 iE
Ψ is the product of a time-dependent function e and a

position-dependent functionψ

If Ψ=F(x)×F'(t)

The time variations of all wave functions of particles acted on

by stationary forces have the same form as that of an

unrestricted particle.
  t
 iE
∵ substituting   e into time-dependent eq
  2  2
 i   U
t 2m x 2
 iE t   2  iE  t  2  iE t
 Ee   e  Ue 
2m x 2

  2m
2
 2  2 E  U   0
x 

Steady-state Schrodinger eq in 1-D

 2  2  2 2m
   E  U   0
x 2 y 2 z 2  2 3-D

74
** For Schrodinger’s steady-state eq, if it has one or more

solutions for a given system, each of these wave functions

corresponds to a specific value of energy E.  energy

quantization

 Considering standing waves in a stretched string of length L

that is fixed at both ends.

 these waves are subject to the condition(boundary condition)

that y=0 at both ends.


∵φ & need to be continuous, finite, and single-value
x

 λn=2L/n+1 , n=0,1,2,3……

 combination of wave eq & boundary condition.

 y(x,t) can exist only for certainλn

Eigenvalues & Eigenfunctions

The value of energy En for which Schrodinger’s steady-state eq

can be solved are called eigenvalues and the corresponding

wave functions φn are called eigenfunctions.

 The discrete energy levels of H atom

 me4  1 
En   , n  1,2,3,..........
32 2 o  2  n 2 
2

75
are an example of a set of eigenvalues.

In addition to E, angular momentum L is also quantized. In H

atom, the eigenvalues of the magnitude of the total angular

momentum are L  l i  1 , l  0,1,2,3............(n  1)

 A dynamic variable G may not be quantiaed.

 measurements of G made on a number of identical systems

will not yield a unique result but a spread of values which

average is expectation value.


G   G  dx
2



for example, in H atom, position x is not quantized.

76
5.6 particle in a box

 the motion of a particle is confined

between x=0 & x=L by infinitely hard

wall(it U(0)=U(L)=∞)

 A particle does not lose energy when

it collides with hard walls.

 U(0<x<L)=0=constant

 φis 0 for x  0 & x  L

within the box: d 2  2m2 E  0( U  0)........(5.24)

2

dx 

eq(5.24) has the solution

2mE 2mE
  A sin x  B cos x
 

B.C. φ=0 at x=0 & x=L

∵cos0=1 B=0 (∵φ(x=0)=0)

2mE
 ( x  L)  0  L  n n=1,2,3,……….


 energy of particle can have only certain values

eigenvalues energy levels

En= n 
2 2 2

n=1,2,3……….
2mL2
2mEn
 n  A sin x

n 2 2 nx
 En    n  A sin (eigenfunct ions )
2mL L

77
 these eigenfunction meet all requirements
 n
φn is a finite, single-valued, and n & continuous
x

(except at the ends of the box)

 To normalize φ

  dx  1
2
n


 nx 
L L
   n dx  A2  sin 2 
2
dx
0 0  L 
A2   2nx  
L L
  dx   cos dx 
2 0  L  
0
( sin 2  
1
1  cos 2  )
L 2
A2   L  2nx  L
  x   m  sin   A2    1
2    L 0 2
2
 A
L
2 nx
 n  sin , n  1,2,3.........
L L

10

78
 2 nx
* n  sin
L L

φn may be “-“ , but n

2
is “+”

(∵ n
2
is probability density of

finding the particle)

*when n=1 , the particle most likely to

be in the middle of the box but when

n
2
n=2 , =0 in the middle of the box.

Ex 5.3

Find the probability that a particle

trapped in a box L wide can be found

between 0.45L & 0.55L

For n=1 & n=2

11

79
Classically, we expect the particle to be in this region 10% of

the time ( 0.55  0.45L  0.1 ) but QM gives different prediction

L

depending on n
x2

Px1 , x 2  
2
n dx
x1

2nx
x
2 2
  sin 2 dx
L x1 L
2nx  2
x
x 1
  sin
 L 2n L  x1

∴ for n=1 , Px1 x2=19.8%

n=2 , Px1 x2=0.65%

12

80
ex 5.4

Find <x> of the position of a particle trapped in a box L wide

L
  2nx  


2

2 x

2

x sin  
 L   cos 
2nx
L


 
x dx

L : 4 4 n  8 n
2

<x>=   L L 
  0
2
2L L
 x    
L 4 2

Middle of the box !!

13

81
 5.7 finite potential well

*Potential energies are never ∞

consider potential wells with barriers of

finite height

*Particle energy E<U

classical mechanics: when particle strikes

the side of the well, it bounces off

without entering regions In QM, it has a

certain probability of penetrating into

regions Ⅰ&Ⅲ

*In Ⅰ&Ⅲ
 2 2m
 E  U   0
x 2  2
d 2
2
 a 2  0 x<0 , x>L
dx

2mU  E 
a

    Ae ax  Be  ax

ax -ax -ax
φⅢ = Ce +De ∵e ∞ when x -∞
ax
e ∞ when x ∞
ax -ax
∴ B=C=0  φⅠ=Ae , x<0 φⅢDe ,x>L

14

82
** these wave functions decrease exponentially inside the

barrier.

Within the well

2mE 2mE
 E sin x  F cos x
 φⅡ  

∵φ is continuous

∴φⅠ(x=0)=φⅡ(x=0) φⅡ(x=L)=φⅢ(x=L)
-aL
∴ A=F = De

 solve E (E≠0)

at x=0 & x=L is continuous
x

combining these B.C.  solve complete wave function

**Because the wavelengths that fit into the well are longer than for

an infinite well of the same width  particle momentum are lower

(∵P=h/λ)  En are lower than they are for a particle in an

infinite well  The wave function penetrates the walls, which

lowers the energy levels.

15

83
5.8 Tunnel effect

Particle strikes a potential U(E<U) the barrier has finite width (see

Fig 5.8)  particle has non-zero probability to pass through the

barrier & emerge on the other side.

Ex: tunnel diode: e' pass through potential barrier even though their

KE<barrier height

 In region Ⅰ&Ⅲ U=0

d 2  2m
 2 E   0
dx 2 

d 2 2m
 E  0
dx 2  2

   Ae ik x  Be ik x
1 1

  Fe ik x  Geik x
1 1
2mE p 2
k1=   (eq 5.43)
 ei  cos  i sin    
e  i  cos   i sin 

∴eq 5.43 the same as particle in a box

1  Aeik x 1
represents incoming wave

1  Be ik x 1
represent reflected wave

16

84
  φⅠ=φⅠ+ +φⅠ-

φⅢ+ = Fe ik1 x represented transmitted wave in region Ⅲ nothing

could reflect the wave

G  0  φⅢ=φⅢ+= Feik x 1

17

85
  v1= is the group velocity of incoming wave (equal to v of

particles)

 S  1 v 
2

is the flux of particles that arrives at the barrier,

# m
S= # of particles/m2sec ( )
m3 sec

 Transmission probability
2
  v FF * v 
T 
2
  v AA * v

classically T=0 ∵E<U

In region Ⅱ Sch eq
d 2  2m
 2 E  U    0
dx 2 
2 m E  U 
   Ce  k x  Dek x , k2 
2 2

(same as finite potential well)

∵exp are real quantities  φⅡ does not oscillate and   2 is not zero

 particle may emerge into Ⅲ or return toⅠ

18

86
 
applying B.C. & need to be continuous
x
  
d   d 
at x=o  (see Fig 5.9)
dx dx

at x=L φⅡ=φⅢ

dφⅡ/dx =dφⅢ/dx

 A+B=C+D

ik1 A  ik1B  k2C  k2 D

Ce  k 2 L  Dek 2 L  Fe ik1 L
 k2Ce  k 2 L  k2 Dek 2 L

 A  1 i  k k  1 i  k k 
       2  1  e(ik1  k 2 ) L     2  1 eik1  k 2 L
 F   2 4  k1 k2   2 4  k1 k2 

Let’s assume U>>E

2mE k2 k
k1    1
 k1 k2

2m( E  U ) k k k
k2   2 1  2
 k1 k2 k1

also assume L is wide enough  k2L>>1

e k 2 L  e  k 2
 A   1 ik 
      2 eik1  k 2 L
 F   2 4k1 
 A   1  ik 2   ik1  k 2 L
  *    e
 F   2 4k1 

+ - + -
Here vⅢ =vⅠ ∴vⅢ /vⅠ = 1

19

87
  
FF * v 
 AA *  1
16 
T  
      e  2 h2 L
 FF * 
2
AA * v  4   k2  
  k 
 1 
2mU  E  /  2 U
2
 k2 
     1
 k1  2mE /  2 E
approximation   1
 T  e 2k 2 L

20

88
5.9 Harmonic oscillator

Harmonic motion: the presence of a restoring force that acts to

return the system to its equilibrium configuration when it is

disturbed.

In the special case, the restoring force F follow Hook’s law 

2
d 2x h
F=-kx  -kx= m d x
  x0
dt 2 dt 2 m

 x  A cos2t   
1 k
 frequency of harmonic oscillator
2 m

A: amplitude

Φ: phase angle depends on what x is at t=0

In most of cases, restoring forces do not follow Hook’s low, but

when only consider a small displacement of x restoring

force can be exercised by Hook’s low.

 Any system in which something executes small vibrations about

an eqm position behaves like a simple harmonic oscillator.

21

89
.Maclaurin’s series
2 3
F(x)=Fx>0 + ( dF )x=0 X + 1/2( d F
)x=0 X2 + 1/6( d F
)x=0 X3 + ……
dx dx 2 dx 3

∵ x=0 is eqm position  Fx=0=0

2 3
for small x x ,x is much smaller than x  F(x)=(dF/dx)x=0 X

for restoring force (dF/dx)x=0 is negative  Hook’s law

2
.potential energy U(x)=-∫ 0x F(x)dx= k∫ 0x xdx=1/2kx

.sch eq
 2 2 2
+ 2m/h (E-1/2kx )φ=0……(5.75)
y 2
1/2 1/2
let c=(1/h hm ) , y=(1/h hm ) x=cx

 2    y     
=     c 
y 2 x  y x  x  y 

    y  2  
2
= c   
  c y 2
 y  y x 
2  2 2 2
 eq5.75  c +2m/  (E-1/2kx )φ=0
y 2
 2 2
 +2E/  ( m/k φ)- mk /  × x φ=0
y 2

 let α=2E/h( m/k )

 2
∴Sch eq (5.75) 
y 2
 
   y 2   0......5.74

for this eq, when y ∞ φ 0

for ∫  
2
dy=1

22

90
*for(5.78) only when α=2n+1 n=1,n=2,n=3……

can satisfy all conditions

∵α=2E/h( m/k )=2E/hν & α=2n+1

∴En=(n+1/2)hν n=0,n=1,n=2……

energy levels of Harmonic oscillator

Zero point energy E0=1/2(hν) ∴when T 0 E E0 not 0

23

91
 H atom

A particle in a box

A harmonic oscillator

“equally spaced & Eo

≠0”

24

92
for harmonic oscillator

each αn En φn
1
 2m  4 n 21
 
y 2

n    2 n! H n  y e 2

  

φn consists of a polynomial Hn(y)

(Hermit polynomial) see table 5.1

From Fig 5.12, the particle is able to

penetrate into classically forbidden

regions with an exponentially

decreasing probability.

25

93
 Classical: max at end

QM: Max at middle

n=0

QM: n=10

When n

QM classical

When n

penetration

Operators, eigenfunctions & eigenvalues


p   p
2
Is dx ??



E  E
2
dx ??


∵φ=φ(x,t), In order to carry out the integrations

 we need to express P&E as functions of x,t

but px   & Ex  

2 2

∴no function as p(x,t)&E(x,t)

 Integration form is not suitable for <P> <E>

26

94
    Et  px
 i
for free particle   Ae

 i  
 p  p  
x  i x
  i 
 E  E  i 
t  t
 
 P 
 i  x operator

E  i 
t
E  KE  U
1     2 2
2
p2
KE   KE    
2m 2m  i x  2m x 2

  2 2
i  U
t 2m x 2
   2  2
 i   U  sch eq
t 2m x 2
 
  
p     pdx      dx
   i x 

 
  dx
i  x

 
 
E     Edx 

    i t dx



= i     dx
 t

expectation value

of an operator Gx, p      Gdx


eigenvalue eq G n  Gn n

 2 2
H  U
Hamiltonian operator 2m x 2
 H n  En n

27

95
 *Particle in a box
2 nx d 2 n nx
  n  sin  cos
L L dx L L L

   d 
   dx
p     pdx    i dx 
 

 2 n nx nx
L

i L L 0 sin
L
cos
L
dx

0
2 n
E  p  pn   2mEn    momentum
2m L

eigenvalue

± means that the particle is moving back & forth

average pav 
n L   n L  0
L

﹡Find momentum eigenfunction

 d 2 nx
p n  pn n p n  sin
i dx L L

φn is not momentum eigenfunction

 d  2 nx   n 2 nx
  sin  cos  pn n

i dx  L 
L  i L L L
e i  e  i 1 1
sin    ei  e  i
2i 2i 2i

28

96
 1 2 inx L
 n  e
2i L
momentum eigenfunction
1 2  inx L
 n  e
2i L

Varity  n &  n are eigenfunction

p n  pn n
 d   1 2 in inx L n 
n  e   n  pn  n 
i dx c 2i L L L
 n
pn 
L
1 2 inx L
and n can be e
2i L
  n
similar pn 
L

29

97
Ch6

98
 Chapter 6
6.1 Schördinger Equation for H atom

 2  2  2 2m
   E  U   0
x 2 y 2 z 2  2
 e2
electric potential energy U 
40 r

∵U is function of r, rather than x,y,z

 1. Express U in terms of x,y,z

 2. Express Schördinger Equation in terms of r,θ,φ, ( see

fig 6.1 )

Owing to the symmetry of physical situation

=>choose spherical polar coordinates.

r = length of radius vector from O to P

= x2  y2  z2

θ= angle between radius vector and z axis

z
= cos 1 ( zenith angle )
x2  y2  z2

ψ= angle between the projection of radius vector in x-y plane

and the x axis

y
= tan 1 ( azimuth angle )
x

99
*In spherical polar coordinates, Schördinger Equation

1   2   1     1  2 2m
r   sin    E  U   0
r 2 r  r  r 2 sin      r 2 sin   2  2

substituting U & multiplying r 2 sin 2 

  2        2 2mr 2 sin 2   e2 
sin   r
2
  sin   sin      E   0
r  r       2 2  40 r 

------(6.4)

 solve eq(6.4) for φ => get three quantum number

*A particle in a three-dimensional box needs three quantum

numbers for its description

∵there are three sets of B.C., φ must be zero at the walls of

box in x,y,z.

In H atom, the e’ motion is restricted by the inverse-square E field

=> but e’ is nevertherless free to move in 3-D => need 3 quantum

number.

100
6.2 Separation of Variables

The advantage of writing Schördinger Equation in spherical polar

coordinates for H atom is that it may be separated into three

independent eq.s, each involving only a single coordinate.

i.e. we would like to have

 r, ,   Rr   

 R dR
    
r r dr
  d
  R  R
  d
 2  2 d 2
  R 2  R 2
 2  d

 Schördinger Equation

sin 2  d  2 dR  sin  d  d  2mr 2 sin 2   e2   1 d 2

r   sin     E  
R dr  dr   d  d  2  40 r   d
2

This eq. can be correct only if both sides of it are equal to the

same constant, since they are functions of different variables.

*It is convenient to call this constant me2

 1  2
 me2
  2

for right-hand side of eq(6.7), divided eq. by sin2θ

3

101
1 d  2 dR  2mr 2  e 2  me2 1 d  d 
r   2   E     sin  
R dr  dr    40 r  sin   sin  d 
2
d 

Again, we have an eq. in which different variables appear on each

side => both sides equal to the same constant. This constant is

called   1

me2 1 d  d 
   sin      1
sin 2   sin  d  d 
1 d  2 dR  2mr 2  e 2 
r   2   E     1
R dr  dr    4 0r 
d 2
  me2  0 eq. for Φ
d 2

1 d  d   me2 
 sin      1  2   0 eq. for Θ
sin  d  d   sin  
1 d  2 dR   2m  e 2    1
 r      E    R  0 eq. for R
r 2 dr  dr    2  40 r  r 2

=> φ can be separated into RΘΦ, only R is dependent on U.

102
6.3 Quantum Number

for Φ (eq(6.12)) =>    Aeim  e

∵Φ need to be single value

      2 
 Aeim   Aeim 2 
e e

 me  0,1,2,3,....   me ：magnetic quantum number

for Θ(θ) (eq(6.13)) =>  is an integer equal to or greater than

me (set the max of me )

 ：orbital quantum number

for R(r) (eq(6.14)) En can be “+” or

 me4  1  E
En    n=1,2,3,…
32 2 02  2  n 2  n 2

same formula for energy lecels of H atom in Bohr mode.

n：principlr quantum number

n must be equal to or greater than  1

=>  =0,1,2,3,…,(n-1)

  Rnl m  m
 

The wave functions R,Θ,Φ,φ are given in Table 6.1

103
6.4 Principle quantum Number (Quantization of energy)

In planetary motion, two quqntities qre conserved

－scalar total energy & vector angular momentum

Classically, the total energy can be any value, but it must be

negative if the planet is to be trapped in solar system.

In Q.M. of H atom => the electron energy may have any positive

value (corresponding to an ionized atom) , the only negative

E1
values are En 
n2

=> n → Quantization of electron energy

104
7

105
6.5 Orbital Quantum Number (Quantization of Angular

Momentum Magnitude)

eq(6.14) for R(r)

1 d  2 dR   2m  e 2    1
 r 
    E   R  0
r 2 dr  dr    2  40 r  r 2

E includes the e’ kinetic energy of orbital motion which should

have nothing to do with its radial motion.

E=kEradial+kEorbital+U
 e2

40 r
Inserting this expression into eq(6.14)

1 d  2 dR  2m   2   1
=> 2  r  kEradial  kEorbital  R  0 …(6.19)
r dr  dr   2  2mr 2 

 2   1
if kEorbital 
2mr 2

 eq(6.19) is a differential eq. for R(r) that involves functions of

the radius r only.

L2
∵ kEorbital  L  m orbital  r
2mr 2
L2
=> kEorbital 
2mr 2
L2  2   1
=> 
2mr 2 2mr 2

106
=> L    1 (  =0,1,2,3,…,(n-1))

the angular momentum is quantized.

*Resignation of Angular Momentum States

 =0,1,2,3,4,5,6,…

s,p,d,f,g,h,i,…

d state has angular momentum 2(2  1)  6

4s => n=4,  =0

5d => n=5,  =2

Magnetic Quantum Number

＊Orbital quantum number  determines the magnitude L of the

e’ angular momentum.

＊However, angular momentum is a vector → need to specify

the direction

＊The way to determine the direction of L => right-hand rule(see

fig(6.3))

An e’ revolving about a nucleus is a minute current loop →

107
magnetic dipole.

=>when an e’ that possesses angular momentum interacts with an

external magnetic B field.

=>magnetic quantum number me specifies the direction of L by

determining the component of L in the field direction.

=>This phenomenon is space quantization.

If B direction // z direction

=> Lz  me  , me  0,1,2,...,

possible value of me for given  range from +  to -  .

=>number of possible orientations of the angular momentum L in

the magnetic field is 2  +1

The space quantization of orbital angular momentum of H atom is

shown in fig(6.4)

L can never be aligned exactly parallel or antiparallel to B

∵Lz is always smaller than   1

In the absence of an external magnetic field, the direction of z is

arbitrary but L in any chosen direction is me  .

10

108
＊Why is only one component of L quantized?

L can never point in any specific direction but instead is

somewhere on a cone in space such that its projection Lz is me  .

Were this not so, => uncertainty principle would be violated.

If L were fixed in space => Lx,Ly,Lz had definite values => e’

would be confined to a definite plane.

Ex. if L were in z direction => e’ would have to be in x-y plane

(fig(6.5)) => ΔZ=0 => ΔP →∞

It’s impossible if it is to be part of H atom number.

∵ only one component Lz & magnitude of L have definite

value, and L  Lz , the e’ is not limited to a single plane (see

6.5,6.6) => ΔZ uncertainty

∵ the direction of L is not fixed (fig(6.6))

 average of Lx & Ly = 0 but Lz  me 

11

109
12

110
6.7 Electron Probility Density

In Bohr’s model：e’ revolves around the nucleus in a circular path.

(fig(6.7))

 the e’ would always be found a distance of r = n2a0 from

nucleus and θ=90º, while ψ changes with time.

Q.M.：

(1) No definite values of r,θ or ψ can be given, only relative

probabilities for finding e’ => wave nature of e’.

(2) We can’t even thick of e’ as moving around the nucleus in

independent of time and varies form place to place.

13

111
 R  
2 2 2 2

    Aeim  e

  *  A2 e  im   eim   A2
2
e e

The probability of finding e’ is independent of ψ =>

probability density is symmetrical about the z axis.

*
2
for s state is a constant

∵ is also a constant => 

2 2
is spherically symmetric for s

state：it has the same value at a given r in all direction

*e’ in other states do have angular preference. See fig(6.12)

∵
2
is independent of ψ, we can obtain a three-dimensional

picture of 
2
by rotating the representation about a vertical

axis.

*For 2p state me  1=> like doughnut in the equatorial plane

centered at nucleus. The most probable distance = 4a0 = the radius

of Bohr orbit for n=2.

14

112
Similarly, 3d with me  2 , 4f with me  3

*Bohr model predicts the most probable location of e’ in one of

several possible states in each energy level.

R depends on r and n, 

R is a max at r = 0 for all s states, which correspond to L = 0 ( ∵

 =0)

The value of R = 0 at r = 0 for the states with  > 0.

Probability of finding e’ probability of finding e’ in the

infinitesimal volume element dV =>  dV

2

15

113
dV  dr rd r sin d 

=>p(r)dr of finding e’ in spherical shell between r & r+dr

pr dr   R 2   dV
2 2

 2
 r 2 R dr 0  sin d 0  d
2 2 2

 r2 R
2
(∵ Θ & Φ are normalized function)

fig(6.11) => p(r)dr

Curves are quite different
fig(6.8) => R

p is not max at r = 0, as R is, but has its max a definite distance

from it.

16

114
The most probable value of r for  s e’ = a0 the orbital radius of a

gound-state e’ in Bohr model.

However , average value of r for  s e’ is 1.5a0 but average value

1 1
of is
r a0

=> energy level for Q.M. = Bohr models

17

115
6.8 Radiative Transitions

In Bohr model, an atom dropping from Em to En

 frequency ν of radiation emitted

Em  En
 
h

Time-dependent wave function Ψn in a state of quantum number

n & energy En is the product of a time-dependent φ n &

time-varying function

 n  En h

 n   n e  i E n  t
n*   n*eiE n  t

 i E n i E n  t
=> x   xn* n dx   x n* n e 
    
dx

  x n* n dx


 x is constant in time (∵  n* &  n are function of x)

 The electron does not oscillate

 No radiation

 Q.M. predict that a system in a specific quantum state does

not radiate.

18

116
＊consider e’ shift from one state to another, e.g.

State n excite State m radiate State n

Ground state Excited state

Ψ can exist in both state n & m =>

Ψ=aφn+bΨm

aa* ≡ probability in state n

aa*+bb*=1
bb* ≡ probability in state m
excite radiate
initially a=1 & b=0 b=1 & a=0 a=1 & b=0

while e’ is in either state => no radiation in the midst of transition

from m to n

 a, b are non-zero => EM waves produced

x   xa * n*  b*m* an  b m dx



  xa 2 n*n  b*a m* n  a *bn* m  b2 m* m dx



 a  x n* n dx  b2  x m* m dx  b*a  x m* ei  E  n e  i  E  t dx

    t
m n

 a *b x n*ei  E  t m e  i  E

  t
n n
dx

last two terms

 E  En  
 i sin  m t  xb a m n  a b n m dx
* * * *

  

19

117
  E  En  
cos m t  xb a m n  a b n m dx
* * * *

  
for real part, it varies with time

 E  En   Em  En 
cos m t  cos 2  t  cos 2t
    h 

 e’ position oscillates at the frequency

Em  En

h

◎When e’ is in state n or m the expectation value of the e’

position between these states, its position oscillates with ν.

=>like electric dipole & radiates EM wavesν.

20

118
6.9 Selection Rules

Forν, we don’t meed to know φn, φm, a, b

But if we would like to know the chance a given transition will

occur => we need to knowφn, φm, a, b

If  x n m* dx  0  allowed transition



= 0→forbidden transition

In H atom => 3 quantum number needed to specify

initial(n’, ' , m ' ) & final(n,  , m ) states.

 Allowed transition  u nm  n*m dV  0



 

(u represents either x, y or z)

∵ nm are known =>  u nm  n*m dV can be ecaluated



  

=> only   1 the transition is allowed

m  0,1

21

119
6.10 Zeeman Effect

Magnetic dipole in a magnetic field B

 torque τ= uBsinθ = u×B


Um, by definition Um = 0 when  
2
 
 U m   d  uB  sin d  uB cos  u  B
2 2

magnetic dipole tends to align itself with B

The magnetic moment of the orbital e’ in H atom depend on L

The magnetic moment of a current loop

u=IA

22

120
If e’ makes frev/s in a circular orbit of r

=> I = -ef => u = -efπr2

2
L = mvr = m(2πfr)r = 2πmfr

  e 
u   L －：negative charge
 2 m 
(-e/2m)：gyromagnetic ratio

 e 
Um    LB cos
 2m 
L    1

 e 
 magnetic energy U m  m  B
 2 m 
e
：Bohr magneton
2m

uB = 9.274×10-24 J/T

= 5.788×10-5 eV/T

 In a magnetic field, the energy of a particular atomic state

depends on m & n.

 A state of total quantum number n breaks up into several

substates when the atom is in a magnetic field. Their energy

are slightly more or less than the energy of the state in the

absence of field.

23

121
 Individual spectral lines “splitting” into separate lines

 Zeeman Effect

The spacing of lines depends on magnitude of field

m have 2  1 values

∴  split into 2  1 substates in magnetic field energy

difference is uBB

 m  0,1 (selection rule)

 spectral line from transition between 2 states of different

 to be split into 3 components.

＊Normal Zeeman Effect consists of splitting of a spectral line of

24

122
 eB B
ν0 into 1   0    0  uB 
4m h
2 0

eB B
3 0    0  uB 
4m h

ex 6.4

A sample of a certain element is placed in a 0.3T magnetic

field & suitably excited. How far apart are the Zeeman

components of 450nm spectra line of this element?

Sol.

eB
 
4m
c d
 d  c
 2
2  eB2
=>     2.83  1012 m  0.00283nm
c 4mc

25

123
Ch7

124
 Chapter 7
7.1 Electron Spin

＊Fine structure：many spectral lines consist of two separate

lines that are very close to each other.

ex. H atom, first line of Balmer series

n = 3 → n = 2 => 656.3nm

in reality, two lines separate 0.14nm

Zeeman Effect：

From chapter 6, spectral lines of an atom in a magnetic field

→ split into 3 components.

In reality, more components were observed. Anomalous

Zeeman Effect are shown in Fig 7.1

125
 Every electron has an intrinsic angular momentum, called

spin, whose magnitude is the same for all e’. Associated with

this angular momentum is a magnetic moment (proposed by

Goudsmit & Ohlenbeck)

Classical picture：

spins → an electron as a charged sphere spining on its axis.

The rotation involves angular momentum → magnetic

moment opposite to S(angular moment)

∵negative charge

electron spin → solve fine structure & anomalous Zeeman

Effect

126
*From this picture, in order to have observed angular

momentum associate with electron spins => e’ have to rotate

with an equatorial velocity > C (see ex 7.1)

=>Paul Dirac in 1929 found e’ must have intrinsic angular

momentum & magnetic momentum

1 3
s => S  ss  1  
2 2

apin quantum number angular momentum due to e’ spin

*Space quantization of e’ → ms(spin magnetic quantum

number)

1
2s+1=2 orientations => ms   spin up
2
1
ms  
2
1
S z  ms   
2

 e 
spin magnetic moment us  S (gyromagnetic ratio=2 for e’ spin)
m
e
usz     uB
2m

127
 Stern & Gerlach found the initial beam split into two

distinct parts that correspond to the two opposite spin

orientations in the magnetic field permitted by space

quantization.

 A total of four quantum numbers are needed to describe each

possible state of an e’

n, , m ,&ms

128
7.2 Exclusion Principle

For elements that have atomic number 9(F),10(Ne),11(Na)

 chemically different

If all e’ in an atom were in the same quantum state => no way

that chemical properties of elements change so sharply.

*Pauli exclusion principle

No two electrons in an atom can exist in the same quantum

state. Each e’ must have a different set of quantum number

n, , m , ms .

129
7.3 Symmetric & antisymmetric Wave Function

Complete wave function  1,2,3,..., n  of a system of n

noninteracting particles can be expressed as

 1,2,3,..., n    1 2 3... n 

＊consider two identical particles case. One in quantum state a,

the other in quantum state b.

∵particles are identical

 
2
are the same if particles ate

exchanged.

  1,2   2,1
2 2

symmetric  2,1   1,2

antisymmetric  2,1   1,2

If particle 1 is in state a, and particle 2 is in state b, the wave

function of the system is

 I   a 1 b 2

If particle 2 is in state a, and particle 1 is in state b,

   a 2 b 1
II

130
∵ two particles are indistinguishable => no way to know

whether  I or  II describes the system.

The probability for  I = II

 system spends half the time in configuration whose wave

function is  I and the other half is  II

 a linear combination of  I &  II is the proper description

of the system.

Symmetric s 
1
 a 1 b 2   a 2 b 1
2

Antisymmetric A 
1
 a 1 b 2   a 2 b 1
2
1
is needed for normalization.
2

In symmetric case, both particles 1 & 2 can simultaneously exist

in the same state with a=b but in the antisymmetric case, if a=b

=> A 
1
 a 1 b 2   a 2 b 1  0
2

=>Two particles can not be in the same quantum state.

131
Pauli found that two e’ in an atom can be in the same quantum

state.

 systems of e’ are described by wave function that reverse

sign upon the exchange of any pair of them.

*Experiments show that all particles which have odd

1 3 
half-integral spins  , ,...  have wave functions that are
2 2 

antisymmetric to an exchange of any pair of them.

 includes protons & neutrons & e’

 obey exclusion principle

 particles of odd half-integral spin are refered to as fermions

(obey Fermi-Dirac distribution)

*Particles whose spins are 0 or integer have functions that are

symmetric to an exchange of any pair of them.

 include photons, α particles, Helium atoms

 do not obey exclusion principle

 particles of 0 or integral spin are often refered to as bosons

(obey Bose-Einstein distribution)

132
＊Spin-orbit Coupling

○ Fine-structure doubling of spectral lines arises from a

magnetic interaction between the spin & orbital angular

momenta.

○An e’ revolving about a nucleus finds itself in a magnetic

field → magnetic field acts on e’ spin magnetic moment to

produce a kind of internal Zeeman Effect.

um  uB cos  uz B  uB B

○Depending on the orientation of its spin vector, theE will be

higher of lower by uBB than its energy without spin-orbit

coupling.

133
 every quantum state (except s states   0 ) is split into two

substates.

Example 7.3

Estimate the magnetic energy Um for an e’ in the 2p state of

a hydrogen atom using the Bohr model, whose n=2 state

corresponds to 2p state.

Sol：

u0 I
B
2r

The orbiting e’ sees itself circled f times per second by the

proton of charg +e that is nucleus,

u0 fe
=> B 
2r
v
f  and r  n 2 a0
2r
4  107  8.4  1014 s 1 1.6  1019 C 
B
2  2.1  1010 m 

134
 U m  uB B  9.27  1024  J T  0.4T

= 3.7×10-24 J = 2.3×10-5 eV

○Total angular momentum

  
○For atoms with single electron J  L  S

1
J j  j  1 j  s   J z  m j  , m j   j,... j
2
  
○For J , L, S , both magnitude & direction are quantized for

atoms with single e’ j    s => J>L

 
L & S can never be exactly parallel or antiparallel to each

other or to J .

135
136
    
＊ L & S interact magnetically. If no external field => L & S

precess around J

＊If B present => J process about B, while L & S still continue

processing about J. The precession of J about B is what give

rise to the anomalous Zeeman Effect, since different orientation of J

involve slightly different energies in the presence of B.

137
 LS Coupling

When more than one e’ contributes orbital & spin angular

momenta to the total angular momentum J of an atom, J is still

the vector sum of these individual momenta.

Orbital angular momenta Li of various e’ are coupled

together into a single resultant L. Same for Si

 
=> L   Li
 
S   Si
 
The momenta L & S interact via spin-orbit effect to form

a total angular momentum J => LS coupling

  
J LS

L  LL  1

Lz  M l 

138
 S  S S  1

Sz  M s 

J  J J  1

J z  M j

*L & ML are always integers or 0

*other quantum numbers are half-integral if an odd number

of e’ is involved and integral or 0 if an even number of e’

is involved.

*J range from L  S to L+S

 when L>S, J can have 2s+1 values

 when L<S, J can have 2L+1 values

Example 7.5

Find the possible values of the total angular-momentum

quantum number J under LS coupling of two atomic e’ whose

orbital quantum number are  1  1 &  2  2 .

Sol：

See fig 7.19

  
L  L1  L2 all values of L are possible from  1   2 to

1   2

139
 ∴L=1,2,3.

1
The spin quantum number s is always
2

S=1,0.

J can have any value between L  S to L+S

J=0,1,2,3,4.

Term Symbols

Total angular-momentum quantum number L

L = 0, 1, 2, 3, 4, 5, 6
s p D F G H I
A superscript number before the letter (2p, for example) is

used to indicate the multiplicity of the state, which is the number

of different possible orientations of L and S, and hence the

number of different possible value of J. The multiplicity is equal

to 2s+1 for L>S, and is equal to 2L+1 for S>L.

 For L>S case

If s =0 => multiplicity is 1 (singlet state) J=L

1 1
If s = => multiplicity is 2 (doublet state) J  L 
2 2

If s =1 => multiplicity is 3 (triplet state) J=L+1,L,L-1

140
 The total angular-momentum quantum number J is used as a

subscript after the letter

2
=> p 3 (doublet p three-halves)
2

1 3
S  , L=1, J 
2 2

In the event that the angular momentum of the atom arises from

a single outer e’ => principle quantum number n is used as a

prefix.
Ground state of sodium => 32 s 1
2

1 1
 n  3,   0, s  , j 
2 2
It is conventional to denote the above state by 32 s 1 with 2
2

indicating a doublet, even though there is only a single

possibility for J (∵L=0)

Example 7.6
For 32 s 1 & 32 p 1 list possible quantum number n,, j, m j
2 2

fof the outer e’

1 1
Sol： 32 s 1 ： n  3,   0, j  , m j  
2 2 2
1 1
32 p 1 ： n  3,   1, j  , m j  
2 2 2

141
For kα L electron drops to K state.

The L electron experiences a nuclear charge of Ze that is

reduced to an effective charge in the neighborhood of (Z-1)e by

the shielding effect of the remaining k e’

mz  1 e 4  1 1  2 1 1
2

=>      CR  z  1   2 
8 02 h 3  n 2f ni2  1 2 
1

3CRz  1
2

 => E k   10.2eV z  1

2

R=1.07×107 m-1

142
Ch8 Molecules

143
 Chapter 8 Molecules

8.1

 What holds atom together? Electric forced hold atoms

together to form molecules.

 A molecule exists because its energy is less than that of the

wywtem of separate noninteracting atoms.

1. A covalent bond：pairs of e’ are shared by two atoms.

example：H2, the attractive force the e’ exert on the protons is

more than enough to counterbalancd the direct repulsion

between them.

The balance occures at 7.42×10-11 m & E=-4.5 eV

 H2 + 4.5 eV → H + H

144
 By comparison

H +13.6 eV → p+ + e’

Easier to break up a molecule than to break up an atom

2. An ionic bond：one or more e’ from one atom may transfer to

the other and the resulting positive & negative ions attract

each other. ex.：NaCl

In many molecules, an intermediate type of bond occurs in

which the atoms share e’ to an unequal extent. ex：HCl

145
8.2 Electron sharing → The mechanism of the covalent bond

 Consider H 2 molecule：a single e’ bonds two protons.

The eletric field around a proton is in effect a box for e’.

Two nearby protons correspond to a pair of boxes with a

wall between them.

 In classical physics, e’ are not allowed to jump

spontaneously to a neighboring proton.

In Q.M. there is a certain probability that an e’ trapped in

one box will tunnel through the wall & get into the other box,

and tunnel back. => e’ is shared by protons.

146
 The probability of an e’ pass through the region of high

potential energy between two protons depends on how far

apart the protons are.

If proton-proton distance is 0.1 nm => energy 10 -15 s e’ jump

from an proton.

If distance is 1 nm => once per second.

147
 →look like 1s wave function of H

When R~a0,
Enhanced like hood of finding e’
between protons.
=> sharing e’ by protons

→He+ ion 1s wave function of He+

148
 φA does not approach 2p wave
function of He+ which has a node
at the origin.

There is a node between a & b

where φ => reduce likehood of
finding e’ between protons

2p state of He+ is an excited state

1s state is the ground state

H 2 in the antisymmetric state have more energy than

when it is in the symmetric state.

149
System Energy

 For symmetric case

When R is large => electron energy Es = -13.6 eV

The potential energy Up of protons

e2
Up 
40 R

When R = 0 => electron energy Es equal that of the He+ ion

=> E2(4x) that of H atom => Es = -54.4 eV

E stotal  E s  U p  has a min.

150
 For antisymmetric case.

When R = 0 → 2p state of He+

 13.6 eV
2
2p state of He+ → E n z
n2
∵ when R → ∞ => EA → -13.6 eV electron energy ~

const (but small dip) The dip is not enough to form bond.

151
8.4 H2 molecule

 H2 molecule has two e’, both e’ can share the same orbital

(same wave function nm ) if their spins are antiparallel.



 Comparing H 2 & H 2 => bounding energy of H 2 is not

of H 2 ∵repulsion between two e’. In H 2 , (same as H 2 )

symmetric wave function s leads to bound state.

 However, based on exclusion principle, the systems of e’ are

described by antisymmetric wave functions.

But the bound state in H 2 corresponds to both e’ being

described by a symmetrical wave function s =>

contradict.

 The complete wave function 1,2  1,2s1,2

1,2 spatial wave function → e’ coordinates

s(1,2) spin function → spin orientation

 The exclusion principle requires the complete wave function

be antisymmetric to an exchange of both coordinates and

spins, not 1,2 only

  sSA or   ASs

152
 If spins of two e’ are parallel => spin function is symmetric.

=> φ needs to be antisymmetric.

(2)If spins of two e’ are antiparallel => spin function is

antisymmetric =>φ needs to be symmetric.

From detailed calculation of SH eq. => case (2) is the case

for H 2 (see fig 8.8)

 Molecular bonds are classified by Greek letters according to

their angular momenta L about the bond axis (i.e. z axis).

σ corresponds to L = 0, π corresponds to L  

 H2O molecule：one 2p orbital in O is fully occupied by two

e’, the other two 2p orbital are only singly occupied and so

can join with the 1s orbital of two H atoms to form sp

10

153
 bonding orbital. The mutual repulsion between H nuclei

widens the angles between the bond axes from 90º to 104.5º

＊ Hybrid orbital → The way in H2O can not be used for CH4

 A C has two e’ in 2s and once’ in each of two 2p orbital =>

expect CH2 with two sp bonding => not the case. (i.e. 2s

does not participate bonding)

 Linear combinations of both the 2s & 2p atomic orbital of C

contribute to each molecular orbital in CH4

 2s & 2p wave functions are both solutions of the same SH eq.

if the corresponding energies are the same, which is not the

case in isolated C atom.

In an CH4 molecule, the E field experienced by outer C e’ is

affected by the nearly H nuclei => energy difference

between 2s & 2p can disappear.

11

154
 Hybrid orbital that consist of mixtures of s & p orbital occur

when bonding energies are greater than pure orbital. In CH 4,

hybrid orbital are mixture of one 2s & 3 2p orbital => sp3

hybrids.

12

155
8.6 Rotation Energy Levels

Molecular energy states arise from (1)the rotation of a molecule

as a whole (2)vibrations of its atoms relative to one another

(3)changes in its electronic configuration

(1) Rotational states are separated by quite small energy

intervals (~10-3 eV)

→ microwave region (0.1mm~1cm)

(2) Vibrational states separated by ~0.1eV → infrared region

(1um~0.1mm)

(3) Molecular electronic states separated by ~eV → visible &

UV region

 For diatomic molecules

The moment of inertia of this molecule about an axis passing

through its center of mass => I  m1r12  m 2 r22

From the definition of center of mass => m1r1 =m2r2 =>

m1m 2
I r1  r2 2  m' R 2
m1  m 2

13

156
 m1 m 2
 reduced mass m' 
m1  m 2

Angular momentum L

L =Iω (ω：angular velocity)

L is quantized

If we denote rotational quantum number J

=> L  JJ  1 J = 0,1,2,3,…

1 2 L2 JJ  1 2
rotational energy levels E J  I   (see ex
2 2I 2I

8.1)

 Rotational spectra：arise from transitions between rotational

energy states.

Only molecules that have electric dipole moments can

absorb or emit photons.

For a rigid diatomic, the selection rule for rotational

transitions is J  1

14

157
In practice, rotational spectra are always obtained in absorption.

E EJ 1  EJ 
J J 1    J  1 => equally spaced.
h h 2I
From the data, I can be calculated. Bond length in molecular can

be got. (see ex 8.2)

15

158
8.7 Vibrational Energy Levels (for diatomic molecule)

 Near the minimum of U-R curve (fig 8.18) → parabolic

1
=> U  U 0  k R  R 0 
2
R0：equilibrium separation
2
dU
F  k R  R 0  => interatomic force (restoring
dR

force)

16

159
 Classically, the frequency of vibrating body of m connected

1 k
to a spring of force constant k is  0 
2 m
1 k m1 m 2
For two-body oscillator  0  m' 
2 m' m1  m 2

 1
For harmonic oscillator E     h 0
 2

ν：vibrational quantum number ν：0,1,2,3,…

1
The lowest vibration state ν = 0 => E 0  h 0  0 =>
2

uncertainty principle.

If oscillating particle were stationary =>Δx =0 =>Δp →∞

 vibrational energy levels

 1 k
E v   v  
 2 m

The higher vibrational states do not obey above eq.

∵potential energy curve is not parabolic.

=> spacing between adjacent levels of v for higher vibration

states.

 selection rule for vibrational states

  1
see Ex 8.3

17

160
＊ Vibration-Rotation Spectra

Pure vibrational spectra are observed only in liquid where

interactions between adjacent molecules inhibit rotation.

∵Evibration >> Erotational => freely moving molecules in a gas

are rotating

The spectra of molecules do not show isolated lines

corresponding to each vibrational transition, but a large

number of closely spaced lines due to transitions between

the various rotational states. => vibration-rotation band

 To a first approximation, the vibrations & rotations of a

molecule take place independently of each other

18

161
  1 k 2
For diatomic molecule E vJ   v    JJ  1
 2  m' 2I

 For v = 0 → v =1 transitions


 The spacing between p & R branch is  
2I

 moment of inertia of a molecule can be found from its IR

vibration-rotation spectrum (or from microwave

pure-rotation spectrum)

vibrational spectra a valuable tool indeterming molecular structures.

19

162
For example, thioacetic acid

Either CH3CO-SH or CH3CS-OH

IR absorption spectrum contains a line at frequency equal to

vibrational frequencies of /\ C  0 and  SH group.

=> confirm CH3CO-SH.

20

163
21

164
8.8 Electronic Spectra of Molecules

The molecule’s e’ can be excited to higher energy levels.

Electronic transitions involve radiation in visible or UV parts of

spectrum. Each transition appears as a series of closely spaced

lines, due to the presence of different rotational & vibrational

states in each electronic state.

A molecule in an excited electronic state can lose energy

and return to its ground state in various ways.

(1)emit a photon of the same frequency as that of the photon it

absorbed.

→returned to ground state in a single step.

(2)fluorescence：molecule gives up some of its vibrational

energy in collisions with other molecule.

=>downward radiative transition originated from a lower

vibrational level in the upper electronic state.

=>Fluorescent radiation is therefore of lower frequency than

that of the absorbed radiation

22

165
 In molecular spectra

Radiative transition between electronic states of different

total spin are prohibited.

 From triplet to singlet transitions have long half-lives result

in phosphorescent radiation.

23

166
Ch9

167
 Chapter 9

9.1 Statistical Distributions

 number of particles of energy ε

n(ε) = g(ε)f(ε)

g(ε) = number of states of energyε

= statistical weight corresponding to energyε

f(ε) = distribution function

= average number of particle in each state of energyε

= probability of occupancy of each state of energyε

 Three different kinds of particles

(1) Identical particles, distinguishable, ex：molecules of gas

little or negligible overlap for wave functions =>

Maxwell-Boltzman distribution

(2) Identical particles of 0 or integer spin, indistinguishable

wave function overlap. => bosons, not obey exclusion

principle. => bose-Einstein distribution. ex：photons =>

symmetric wave function.

168
 1 3 5
(3) Identical particles of odd half integer spin ( , , ,…)
2 2 2

indistinguishable => fermions. Obey exclusion principle

=> Fermi-Dirac distribution, ex：e’ =>antisymmetric

wave function

169
9.2 Maxwell-Boltzman Statistics

For classical particles

f MB   Ae   kT average number of particles f MB   in a

state of energyε

A：depends on number of particles in system analogous to

normalization constant

k =1.381×10-23 J/K =8.617×10-5 eV/K

=> n  Age   kT total number particles that have energyε

see ex 9.1 & 9.2

170
9.3 Molecular Energy in an Ideal Gas

Consider a continuous distribution of molecular energies instead

of discrete set 1 ,  2 , 3 ,...

If n(ε)dε is the number of molecules whose energies lie

betweenε&ε+dε

=> n d  gdf   Age   kT

d

first find g(ε)dε, number of states that have enegy betweenε

&ε+dε

A molecule of energyεhas a momentum P whose magnitude p

is specified by

p  2m  p 2x  p 2y  p 2z

each set of momentum components px, py, pz specifies a

different state of motion.

＊ Consider momentum space, see fig 9.1,

Number of states g(p)dp with momentum whose magnitude

are between p & (p+dp)

4

171
 => g(p)dp  4π2p·dp = Bp2dp (B：constant)

∵each p → single energyε

 g(ε)dε betweenε & (ε+dε) the same as g(p)dp

 g(ε)dp = Bp2dp

md 
∵p2 = 2mε => dp 
2m

 g d  2Bm

3
2
d

 n d  C e

kT
d ( C  2m3 2 AB  cons tan t )

 To find C,

N  0 n d  C0

  
e kT
d

 1  1
 0 xe ax dx  a
2a a kT
C 2N
 kT 2
3
=> N  => C 
kT  2
3
2
2N
 n  d 

e kTd
kT  2
3

see fig 9.2

172
Total energy E  0  n  d


2N  3 2  kT
 3 0  e d
kT  2

2N 3 
  4 kT 2
kT 
kT  2
3

3
 NkT
2
3
 average molecular energy   kT independent of
2
1
molecule’s massεat RT~0.04 eV  eV
25

173
*Distribution of Molecular Speeds

1
  mv 2 dε=mvdv
2
3
 m  2 2 mv
=> n v dv  4N  ve
2
2 kT
dv see fig 9.3
 2 kT 
1 3 3kT
  mv 2  kT => v rms  v 2 
2 2 m

dvv 
*Most probable speed 0
dv

2kT
=> v p  (smaller than v & v2 )
m

*Consider two particle 1,2,

two states 1,2,

I  a 1b 2
for distinguishable particle
II  a 2b 1

for Bosons B 
1
a 1b 2  a 2b 1 symmetric
2
7

174
 for Fermions F 
1
a 1b 2  a 2b 1
2

antisymmetric

*Consider both particles in the same state a

(1) for distinguishable particles, both I & II become

M  a 1a 2

 M M  a 1a 2a 1a 2

(2) for bosons

B 
1
a 1b 2  a 1a 2  2 a 1a 2
2 2

 2a 1a 2

BB  2a 1a 2a 1a 2  2M M

 the presence of particle in a certain quantum state

increases the probability that other particles are to be

found in the same state.

(3) for fermions

F 
1
a 1a 2  a 1a 2  0
2

 the presence of particle in a certain state presents any

sther particles from being in that state.

175
*Bose-Einstein distribution

1
f BE    
e e kT
1

*Fermi-Dirac distribution

1
f FD     α：depends on properties of system and

ee kT
1

may be function of T

*Whenε>>kT, both case → MB

1
*When ε=-2kT, f FD   
2

This energy is called Fermi energy  f  kT

1
=> f FD   
e    F  kT
1

176
*Consider T = 0

1
Forε<εF, f FD  1
e 1


1
Forε>εF, f FD  0
e  1

*at T = 0, all energy states up toεF are occupied, and none

aboveεF

The highest state to be occupied have energyε=εF

See fig 9.6 & table 9.1

10

177
*Rayleigh-Jeans formula (for black body radiation)

Radiation must consist of standing em waves

 a node needs to occur at each wall in any direction

 the path length from wall to wall = an integer number j of

half-wavelengths.

2L
jx   1,2,3,...

2
2L  2L 
jy   1,2,3,... => jx  jy  jz   
2 2 2

   
2L
jz   1,2,3,...


11

178
 To constant number of standing wave g(λ)dλ within the

cavity whose wavelengths lie betweenλ&λ+dλ

 constant number of permissible sets of jx, jy, jz values

If j is a vector from the origin to a particular point jx, jy, jz,

its magnitude is j  j2x  j2y  j2z

1
g jdj  2 4j2 dj  j2 dj
8
Only count first Octant
Two perpendicular directions of polarization

2L 2L 2L
j   dj  d
 c c

 2L  2L 8L3 2
2

g d    d  3  d
 c  c c

The cavity volume is L3

 density of standing waves in a cavity

1 82 d
G d  3 g d 
L c3

＊ Classical Theory

Use oscillator => average energy   kT

 u d  G d

82 kTd 
 Rayleigh-Jeans formula.
c3
12

179
 u(ν)↑ withν2↑ => wrong !!

*Planck radiation law

assume oscillators’ energy εn=nkν

he used Maxwell-Boltzman distribution

 n
number of oscillators with energy  n  e kT

h
  h
e kT
1
8h  3d
 u  d  G d  3 h
c e kT  1

＊ Harmonic oscillator have energy

 1
 n   n  h , not nh 
 2

1
including zero-point energy h
2
h
  is not equal to h
e kT
1

if MB statistics are used.

 consider em waves in a cavity as a photon gas subject to

Bose-Eistein statistics.

13

180
 The average number of photons f(ν) in each state of energy

ε=hν is given by B-E statistics.

Photon distribution function

1
f    h (α= 0)
e kT
1
 u d  hG f  d

8h  3d
 3 h
c e kT  1

○ Wien’s Displacement Law

Find λmax at given temperature for which the energy

density is the greatest.

 solve du(λ)/dλ= 0 for λ=λmax

hc
  4.965
kT max

hc
  max  T   2.898  103 m  K
4.965

 the peak in the blackbody spectrum shifts to shorter

wavelengths (higher frequency) as the temperature is

increased.

14

181
*Stefan-Boltzman Law

Total energy density u

85 k 4 4
u  0 u  d 


3 3
T  aT 4
15c h

total energy density  T 4

 radiated energy R by an object per second per unit area is

 T4
 Stefan-Boltzman Law： R  eT 4

ac
  5.67  108 W m 2  K 4
4

The emissivity e depends on the nature of radiating surface.

15

182
 9.7 Specific Heats of Solids

Molar specific heat of a solid at constant volume Cv

 energy that must be added to 1 Kmol of the solid, whose

volume is held fixed, to raise its temperature by 1 K.

 The internal energy of a solid, resides in the vibrations of its

constituent particles. These vibrations may be resolved into

components along three perpendicular axes. => use three

harmonic oscillators.

 Each atom in a solid should have 3kT of energy.

 Classical internal energy of solid

E = 3N0kT = 3RT

 E 
 C v     3R  5.97 kcal mol  K (Dulong-Petit law)
 T  v

＊ However, for light elements as B, Be, C

Cv << 3R at 20℃

And when T → 0 all solid Cv → 0

See figure at P.320

16

183
Einstein’s Law

The basic flaw for Dulong-Petit Law → kT for 

Einstein proposed average energy per oscillator 

h
  hf    h (average phonon energy per one
e kT
1

direction by Debye model)

 internal energy of solid

3N 0 h
E  3N 0   h
e kT
1
h
 E   h 
2
e kT
C v     3R   h
 T  v  kT  e kT  1
2
 
○ at high temperature, hν<<kT

h h
 e kT
 1
kT
   kT  Cv  3R (Dulong-Petit values)

at high T, the spacing hν between possible energies is

small relative to kT =>εis almost continuous

 classical physics holds.

*at T↓↓ => Cv↓

∵when T decreases, spacing between possible energies↑↑

inhibits the possession of energies above zero-point energy

17

184
Why the zero-point energy does not enetr this analysis?

 E  1
∵ C v    zero-point energy  0  h  function of T
 T  v 2

18

185
9.8 Free Electron in Metal

*If e’ behave like the molecules of an ideal gas => each would

3
have kT , kinetic energy
2
3 3
 Ee  N 0 kT  RT
2 2

 E  3
 C ve   e   R
 T  v 2
3 9
 total specific heat C v  3R  R  R at high T
2 2

But, 3R holds for high T. Why?? e’ do not contribute to Cv

*for e’, average occupancy per state

1
f FD       F 
e kT
1
now, we would like to find g(ε)dε,number of quantum

states available to e’ betweenε&ε+dε

same as number of standing waves.

g(j)dj = πj2dj

2L h
j for e’   & p  2mE
 p

2L 2Lp 2L 2mE L 2m
j   dj  d
 h h h 
19

186
 8 2L3 m
3

 g d 
2

d
h3
8 2Vm
3

 g d 
2

d
h3

*Femi energy

Εf = highest state to be filled

∵each state is limited to one e’

16 2Vm 2 3 2
3

∴ N  0 g d 
f
f
3h 3
2
h 2  3N  3

 f   
2m  8V 

(N/V is the density of free e’)

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9.9 Electron-Energy Distribution

n  d  g f  d 

8 2V m 2 h 3 d
3

e    kT  1
f

3

=> n  d 
3 N 2 f
2
d
see fig 9.10
   f 
e kT
1
*The total energy E0 at 0 K

E 0  0 n d
f

e   kT  e   0
f

3N 23  32 3
 E0   f 0  d  N f
f

2 5
3
 average energy for e’ at T = 0  0   f
5

＊ The temperature of an ideal gas whose molecules have an

average kinetic energy of 1 eV is 11,600 K. But εf ~

several eV.

A sample of Cu would have to be at T > 50,000 K for its e’

to have the same energy at T = 0 K.

＊ The failure of free e’ in a metal to contribute appreciably to

Cv is due to the energy distribution.

When a metal is heated, only e’ hear theεf (ε-εf ~ several

kT) can be excited to higher state.

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  2  kT 
 C ve   R
2  f 
at room temperature, kT  0.016  0.0021 very small
f
*Ony if T is very low => Cve become significant ( C v  T 3 but

C ve  T )

*Or if T is very high => Cv →3R but Cve↑↑

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