3

3.1

Other Early Evidence for

Quantum Behavior
Photoelectric effect

Effect: blue light shining on metal observed to kick out electrons, longer
wavelength light doesnt, independent of how intense it is!
Einstein (1905) proposed Planck idea might explain this. Light (like SHO
energies) might come in lumps or quanta of energy h. Suppose electrons in metal have binding energy , then energy of e knocked out
should be
E h
(1)
i.e., photons with frequency < dont carry enough energy.
Richardson & Compton (1912) verified Einstein relation and showed value
of h agreed with Planck!
3.2

Atomic spectroscopy and Ritz principle

Spectrum of radiation from hot gas known since late 19th cent. to consist
of discrete lines at frequencies i
Ritz (1908?) noticed the set of i can be written as the set of differences
among smaller set of frequencies:
i = f f ,

(2)

Agrees with Einsteins concept if atoms have discrete set of energy levels
1

E , and light is produced by transitions among them, of freq.

= (E E )/h

(3)

Atomic hydrogen
Balmer Series (1885): set of optical spectroscopic lines of H at the
set of wavelengths ( = c/) associated with freqs.
1
1
= R( 2 ),
4 n

n = 3, 4, 5...

(4)

n = 3, = 6363A (H )
n = 4, = 4861A (H )
n = 5, = 4340A (H )

Lyman Series (1914): set of ultraviolet spectroscopic lines of H at

= R(1

1
),
n2

n = 2, = 1215A (L )
n = 3, = 1025A (L )
n = 4, = 972A (L )
2

n = 2, 3, 4...

(5)


Paschen series (1908)
1
1
= R( 2 ),
9 n

n = 4, 5, 6...

(6)

1
1
2 ), n = 5, 6, 7...
16 n

(7)

Brackett series (1922)

= R(

Clearly H-atom energy levels vary as 1/n2. Heres a Maple plot of

the Balmer and Lyman series.

6000

5000

4000

3000

2000

1000
0

0.2

0.4

0.6

0.8

3.3

Bohr model

Bohr quantized the classical model of the H atom, namely an electron

orbiting a fixed proton in a circle of radius a. Did so using criterion
3

suggested by Ehrenfest, that angular momentum be quantized:

L=

nh
nh,
2

n = 1, 2, ...

(8)

Classically,
mv 2
e2
centripetal force
= Coulomb force (SI units)
,
a
40a2

(9)

and the L = nh gives

40n2h
2
a=
n2 a 0 ,
2
me

(10)

where the smallest allowed radius, the Bohr radius, is given by

40h
2
a0 =
' 0.5A,
me2

(11)

and the energy is

1 2 e2 e2
E = mv =
2
a
2a

!
m e2 1

=
2
h2 40 n2

(12)
(13)

explains observed spectra remarkably accurately.

3.4

de Broglie wavelength

Is light a particle (Einstein photoelectric effect picture) or a wave (classical

optics)? Prince Louis de B. said in his 3-page PhD thesis:
1. wave phenomena characterized by wavelength = distance between
fronts of constant phase .
4

Plane wave E exp i(k r t):

= k r t = phase of wave
= 2/k = distance to make change by 2
c = /k = phase velocity of wave

(14)
(15)
(16)

2. particle phenomena photons have energy

E =h

(17)

and momentum (relativity!)

E
=h
/c = h
k
(18)
c
Since photon travels in direction of k, take p = h
k in fact. Compton
(1922) found electrons recoil off x-rays (photons) as if x-rays were particles,
energy h
, momentum h
k.
de Broglie: suppose electrons and other particles have a wave nature
like photons, with
p=

E =h
, p = h
k.

(19)

Assume E = p2/2m for nonrelativistic particles, get dispersion relation

(relation between and k)
h
22
h
=
= = h
k 2/2m
2m
5

(20)

Success of de Broglie picture: justification of Bohr-Ehrenfest angular

momentum quantization. Suppose electron viewed as wave moving in
circular orbit around proton. Integral number of wavelengths fit into circle!

But wavelength is length for wave to change phase by 2, so = 2/k =

2h/p,
= h/p de Broglie wavelength
(21)
and angular momentum L = ap = nh/2, so
L = n
h
3.5

(22)

Motion of Wave Packet

de Broglie noted plane waves (r, t) exp i(k r t) can be linearly

superposed to obtain more general wave function representing electron
somehow. 1D example:

(x, t) =

i(kxt)
f
(k)e
dk

h
k2
=
2m
Choose f (k) roughly as shown, centered around k0.
6

(23)

When is (x, t) large? Consider phase = kx (k)t. For most

values of x and t, phase is pure oscillatory as fctn. of k = small. If
however

= 0 at k = k0,
k

(24)

then exp i has a max/min near k0 and will be large!

So condition for to be large is

(kx (k)t), or
k

x =
t,
k
0 =

(25)
(26)

so the peak (pt. of large ) advances with speed /k group velocity vg = h

k/m. Compare to phase velocity Eq. (16), vp /k =
h
k/2m.
Q: What type of wave equation do such strange de Broglie packets
satisfy?
3.6

Expts. Suggesting Wave Nature of Electrons

1. W. Elasser (1925): predicted electrons scattered off a crystal should

show interference pattern, like optical diffraction grating. Observed
by Davisson & Germer.
2. Ramsauer effect. Beam of slow electrons in noble gas has mean free
path expected from known sizes of atoms.

Classical. If is cross-sectional area of atom, line of length L hits all

atoms within cylindrical volume L around it. Contains on avg. Ln
atoms, so mean free path (average distance between collisions) is (n)1.
Quantum. Elasser pointed out electrons would be scattered less if they
really behaved as de Broglie waves, provided dB size of atom. Electrons of suff. small momentum dont see atoms at all!
Classical analog. Q: how can we see through air?
Crude estimates:
8

 What is n, # of air molecules/ vol? Suppose ideal gas, p = nkB T .

Atmos. pressure is 106dynes/cm2, T 300K yields
106
n 16
3 1019atoms/cm3
10 300

(27)

Geometric size of atom: (108cm)2 3 1016cm2.

Mean free path ` 1/(n) 104 cm = photons should be
scattered and attenuated over tiny distance. Must be that wavelength
of light 104A, is so large that atoms dont influence itdoesnt see
atoms.