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Solutions to the Exercies of

C. J. Foots Atomic Physics


Chenchao Zhao
Department of Physics, Beijing Normal University, Beijing, China
(Dated: June 28, 2011)

Early atomic physics


Key formulas:



1
1

n2 n2
mH
RH = R
me + mH
~2
= 0.529 1010 m
a0 =
(Ze2 /40 )me
Ze2 /40 1
E=
Z2
2a0
n2
2
E = 2 E
n
e2 /40
=
= 1/137
~c
f
= R ((Z K )2 (Z L )2 )
c
1
~ 3
() = 2 3
c exp ~/kT 1


N1
~
N2
=
exp
g2
g1
kT
4
2
2
e x0
P =
120 c3
eB
L =
2me
60 me c3
=
e2 2
1
=R

(1.1)
(1.2)
(1.3)
(1.4)
(1.5)
(1.6)
(1.7)
(1.8)
(1.9)
(1.10)
(1.11)
(1.12)

1.1

Isotope shift

To find wavelengths of Balmer- transitions, we set n = 2 and n = 3 as


36
in Eq (??) Then = 5R
, hence
36
(1/RH 1/RD )
5


1
1
36me

=
5R mH
mD
18me
= 0.18 nm

5mH R

H D =

where mD 2mH .

1.2

The energy levels of one-electron atoms

Since (1.4), and let m, n be the quantum numbers of He+ and H, neglecting the isotope shifts, the energy levels in agreement are those with
1/n2 = 4/m2 , namely m = 2n.
Those wavelengths should have the ratio
RHe
H
=
He
RH
mHe (mH + me )
=
mH (mHe + me )
4mH (mH + me )

mH (4mH + me )
1.00041
which is in accord with the data set, 1.00041.

1.3

Relativistic effects

With n = 4, Eq (1.5) gives

E
4
=
= 2 = 75076

for the fact that = ch/E and


d = ch dE/E 2

= (ch/E) (dE/E)

= (dE/E)

This corresponds to a grating of 105 grooves.

(1.13)

1.4

X-rays

Eq (1.7) reduces to f = 3cR Z 2 /4 when Z . Therefore,

1.5

f Z

X-rays

Since E = hf = 3/4(hcR )Z 2 = 13.6 eV 0.75Z 2 , then it predicts


absorptions at around 6.4 keV and 6.9 keV.

1.6

X-ray experiments

See http://www.physics.ox.ac.uk/
history.asp?page=Exhibit10

1.7

Fine structure in X-ray transitions

Energy of the electron in the L-shell should be


E = (82/2)2 13.6 = 22.9 keV
and Eq (1.5) gives
E =

2
E = E/75076 = 0.3 eV
n2

But K transition means an energy of


E = 10.2(Z 1)2 eV = 66.9 keV
then

1.8

E
= 4.5 104 %
E

Radiative life time

Eq (1.10) provides the power of dipole radiation which is rate of change


of energy, for the circular motion, the power doubles since a circular motion
can be decomposed into two linear oscillations,
= E/P = ~

120 c3
1/(er)2 3
2e2 r 2 4

For photons of wavelength 650 nm, = 2.89 1015 rad/s; let r = a0 , the
life time will be 2.7 107 s.

Table 1: Frequency shifts


B [T]
3 105
1
L [MHz]
2.6
8.8 104
L /(1014 Hz) 2.6 108 8.8 104

1.9

Black-body radiation

Setting N2 = 0.1N, N1 = 0.9N, g1 = 1, g2 = 3, Eq (1.9) gives


exp(~/kT ) = 27
provided the wavelength = 600 nm, = 2c/ = 3.131015 rad/s. Therefore, T = 7.23 103 K and Eq (1.8) gives the density
= 4.70 1016 J s/m3

1.10

Zeeman effect

The Larmor frequency is given by Eq (1.11), and the Earth magnetic


field is about 3 105 T, then the frequency shifts are listed in Table 1.

1.11

Relative intensities in the Zeeman effect

One circular motion can be decomposed into to two orthogonal sinusoidal


motions. Let I denote the intensity of three eigen-oscillations of the electron.
Then, we have
Along the magnetic field, only circularly polarized lights can be observed and the intensities are I+ = I = I;
Perpendicular to the magnetic field, motion along z direction and projected horizontal motions can all be observed, and
2I+ = 2I = I = I since the projected horizontal motions are only
half of the circular motions.
Therefore,
(a) Total intensity perpendicular to the field is 2I;
(b) Ratio of intensities received along to perpendicular to the field is
2I/2I = 1.

1.12

Bohr theory and the correspondence principle

Energy of hydrogen atoms takes the form


1
E = K + V = K = me v 2
2
But
me
Then
E=

v2
e2 /40
=
r
r2

1 e2 /40
,
2
r

dE =

e2 /40
dr
2r 2

Hence

e2 /40
r
2r 2 ~
The angular frequency is also given by
= E/~ =

2 =

v2
e2 /40
=
r2
me r 3

Equating the two expressions of , we have


s

r~2
= 2 a0 r
r = 2
2
me e /40
which is equivalent to

r
= 2(a0 r)1/2 .
n
Approximate the equation above by the corresponding differential equa
tion, namely r = 2 a0 r, and the solution turns out to be
r = a0 n 2 .

1.13

(1.14)

Rydberg atoms

Eq (1.4), then
dE
e2 /40 d (n2 )
e2 /40
=
=
= Ry/n3
dn
2a0
dn
a0 n 3
and for n = 50, E = 1.1 104 eV. The radius of such atoms is around
2500a0 or 132 nm according to Eq (1.14).

The hydrogen atom

Key formulas
Ylm (, ) = (1)m
Z

(2l + 1) (l m)! im m
e Pl (cos )
4(l + m)!

(2.1)

d eim ein = 2mn




cos m cos n
d
= mn
sin m sin n

Z
d sin m cos n = 0

(2.2)

(2.3)
(2.4)

d =

sin d =

d(cos )

(j(j + 1) l(l + 1) s(s + 1))


2
1
e2
~2
=
2
2
3
2me c 40 (na0 ) l(1 + 21 )(l + 1)





1 2
1
2
sin
+
L =
sin

sin2 2

Es-o = hS Li =

2.1

(2.5)

(2.6)
(2.7)
(2.8)

Angular-momentum eigenfunctions

From the table of spherical harmonics and Eq (2.2), (2.5), we have


h l1 m| l2 ni 0 if m 6= n, therefore
h 11| 00i = 0
And also
h 10| 00i = (constant)

cos d(cos ) = 0
1

For l = 1, 2, we only need to show that h 10| 20i = h 11| 21i = 0.


Through inspections, the integrands as functions of cos are both odd,
hence the integrals vanish.

2.2

Angular-momentum eigenfunctions

According to Eq (2.1),
l1

Yl,l1 = (1)

2l + 1 i(l1) l1
e
Pl (cos )
4(2l 1)
6

It is convenient to write,
h l, l 1| l 1, l 1i = hl, l| (L ) |l 1, l 1i
= hl, l| L+ |l 1, l 1i
=0

2.3

Radial wavefunctions

With n = 2, l = 1 the integral reads,


  Z
1
1 2
R (r)r 2 dr
=
3
r
r 3 2,1
0
 


Z
Z 5 2 2 2 r/a0
dr

r e
=
r 2a0
3
0
= 1/(24a30 )
Invoking the rhs formula, namely


1
r3

1
=
1
l(l + 2 )(l + 1)

Z
na0

2

(2.9)

yields the same result 1/(24a30 ).

2.4

Hydrogen

The probability is given by


Z rb
Z
r 2 dr |(r)|2 =
0

rb
0

(r/a0 )2 d(r/a0 ) 2r/a0


e

:= ab

y 2 dy 2y
e

0
3 e2 / (rb /a0 )3

The electronic charge density of this region is


e e|(rb /2)|2 =

2.5

e(1 rb /a0 )
a30

Hydrogen: isotope shift, fine structure and Lamb shift

The mass ratio of electron to proton is 5 104 and isotope shift is


of the same order, namely, if = 600 nm, order of isotope shift will be

isotope (5 104 ) (5 105 GHz) = 250 GHz


7

Relativistic effect is of the order of 2 5 105 , then the wave number


difference reads

fs (5 105 ) (5 105 GHz) = 25 GHz


Lamb shift is 1/10 of the fine structure shift, that is

Lamb 2.5 GHz


A Fabry-Perot etalon of finesse F = 100, width d = 1 cm is supposed to
resolve
1

=
= 0.5 3 108 0.1 GHz
(2.10)
n(2d)F
but Doppler effect attenuates the resolution to 0.7 GHz 1 GHz.
Therefore, isotope shift, fine structure can be resolved but Lamb shift
approaches the limit of the apparatus and hence cannot be accurately observed.

2.6

Transitions

From Eq (1.12), we have


Ultraviolet

100 nm

Infrared 1000 nm

2.7

0.45 ns
450 ns

Selection rules

Following similar arguments as in Problem 2.1 and notice there is an


additional cos in the integrand.

2.8

Spin-orbit interaction

Calculations based on Eq (2.6) give


Ej =

l
2

Ej = (l + 1)
2

and the mean of the two is


= (2j + 1)Ej + (2j + 1)Ej = [(l + 1)l l(l + 1)] = 0
E

2.9

Selection rule for the magnetic quantum number

The integral is readily obtained in text of section 2.2.1, and the result
follows the same arguments of Problem 2.1.

2.10

Transitions

(a) The wavefunction takes the form (t, r, ) = A1 eiE1 t/~ + B2 eiE2 t/~
with A B,
1 = R1,0 Y00 , 2 = R2,1 Y1,0
and
||2 A2 |1 |2 + 2|AB||1 2 | cos(12 t)
The second term can be written as
f (r)r cos cos(12 t) = f (r)r z cos(12 t)
= f (r) z cos(12 t)
The sketch of the orbital is as follows (Figure 1)

time

Figure 1: Contour of electron density, or the orbital of wavefunction


(t, r, ) = A1 eiE1 t/~ + B2 eiE2 t/~ with A B, 1 = R1,0 Y00 , 2 =
R2,1 Y1,0 during one period of oscillation.
|i = 1 |i, namely the state exhibits parity, then
(b) If
|i = hri
hri = h| r
hence hri = 0. But the Hamiltonian of hydrogen atom commutes with
then the eigenstates are of specific parities. The only possibility for a
,
none-vanishing hri is to require 1 and 2 to possess opposite parities.
(c)

Now set a0 = 1, the radial integral yields


 5
Z
3
dr
2
1
r 4 e 2 r =
6
6 3
0

The angular integral is exactly 1. The total electric dipole moment is


 5
2
1
ea0 cos t z
eD =
3
6
where a0 is put back through dimension analysis.
9

(d) The density distribution should be more or less similar to Figure 1 for
a constant but it becomes apparent if one writes c = t or
= t c
that a flock of charge is circulating about the z-axis.
(e) The case of (a) is akin to the vertical motion of the electron while (d)
corresponds to right-handed circular motion. The motions are characterized
by the ml but the role of ground state 1s is crucial as pointed out in (b). The
1s state is an exponential decay which binds the electron to the region around
nucleus and hence it is the quantum analogue of the classical restoring force
2 r.

2.11

Angular eigenfunctions: Yll

(a) Raising operator is given as


L+ = ei ( + i cot )

(2.11)

Then we write
( + i cot ) (eim ) = 0
it is equivalent to

cos
=m

sin

(b) The solution is = sinm . Applying L2 (see (2.8)) yields


L2 (eim ) = m(m + 1)eim

2.12

Parity and selection rules

If l1 l2 is even, then
Iang = (1)l1 l2 +1 Iang = Iang
which implies the integral vanishes.
To have non-vanishing angular integrals, l1 l2 must be odd. But the
parity of spherical harmonics is
Ylm = (1)l Ylm

(2.12)

Therefore, the initial and final states must exhibit different parities.

2.13

Selection rules in hydrogen

The wavelengths corresponds to energy 0.306, 0.663, 1.890 eV and they


are transitions from 5 to 4, 4 to 3 and 3 to 2 respectively.
10

3
3.1

Helium
Estimate the binding energy of helium

(a) The total Hamiltonian is the sum of two individual and one interaction
Hamiltonians,
=H
1 + H
2 + H
int
H
2
2
2i Z e
i = ~
H
2m
ri
2
e
int =
H
|r 1 r 2 |

(3.1)
(3.2)
(3.3)

where e2 = e2 /40 .
(b) The energy
E(r) =

Z e2
~2

2mr 2
r

assumes minimum at
rm =

~2
Zm
e2

and it is
E(rm ) =
(c)

Z 2 m
e4
2~2

The repulsive energy, namely electron-electron interaction, is


Eint =

e2
e2
Zm
e4

=
r12
rm
~2

The ionization energy of one electron, according to the estimated energies,


is Eion = 0 But experiment gives Eion = 24 eV, then the average distance
between the two electrons should be greater than rm .
(d) For Si12+ , Eion = (142 14 2) 13.6 = 2285 eV, excluding the
repulsion we have E = 2666 eV. Comparing with results of helium, repulsion
gets irrelevant for larger Z.

3.2

Direct and exchange integrals for an arbitrary system

(a) The direct and exchange integrals are respectively,


Z
e2
J = d3 x1 d3 x2 |u (r1 )|2 |u (r2 )|2
r12
Z
2
e

K = d3 x1 d3 x2 u (r1 )u (r2 ) u (r1 )u (r2 )


r12
11

(3.4)
(3.5)

Yet, |Ai = (2)1/2 (|i |i),


1
(h| h|)H (|i |i)
2
hH i hH i +
=
2

|Ai =
hA| H

Note that

(3.6)
(3.7)


H = H


H = H

Therefore, it holds for real-valued u(r) that


|Ai = H H = J K
hA| H

(b) The symmetric wavefunction is construct as

|Si = (2)1/2 (|i + |i)


The inner product reads
h A| Si =

(1 1 + h | i c.c)
= Im h | i
2

Again, for real u(r), h A| Si are orthogonal.


is invariant under the interchange of particle labels, let
(c) Since H
denote such an operation, then
|Si = hA| H |Si
hA| H |Si = hA| H
|Si = 0.
Hence hA| H

3.3

Exchange integrals for a delta-function interaction

(a) The Hamiltonian is simply the kinetic energy,


H=

~2 2

2m x

For the fact that


u0 = (/l)2 u0

u1 = (2/l)2 u1 ,

then the energies are


E0 =

~2 2
2ml2

E1 =
12

2~2 2
ml2

(b) The direct integral is


 2 Z
2
x2
x1
J=
)ax1 x2 sin2 (
)
dx1 dx2 sin2 (
l
l
l
 2 Z l
2
sin4 (x/l)dx
=a
l
0
Z
4 4 3a
=a
sin x dx =
l 0
2l
The exchange integral is the same thing, K = J. Then the energy shift will
be 3a/l. There is only one state, the symmetric one.
(c)

All the eigenstates takes the form,


r
nx
2
sin
un (x) =
l
l

and trivially Jmn = Kmn since the delta potential identifies the two coordinates. Hence, the antisymmetric state gives no rise to energy shift. Actually,
the antisymmetric part does not exist at all when interaction is considered,
because delta interaction rules out the possibility of no-touch, otherwise
there is no interaction, and hence no energy shift!
(d) See Figure 2.

1
0.6

0.8
0.6
0.4
0.2
0
-0.2
-0.4
-0.6
-0.8

0.2
-0.2
-0.6
-1
1
0.8
0.6

1
0.8

0.4

0.6

x2

0.4

x1

0.2
0.2
00

Figure 2: The horizontal axes are the coordinates x1 and x2 , and the vertical
axis marks the values of function = u1 (x1 )u2 (x2 ).

(e) Possible total spins are 0 and 1. The symmetric spatial functions
corresponds to 0-spin, and the antisymmetric spatial functions should have
spin-1 or spin-0 but they do not exist.

13

(f ) The wavefunctions are independent of particle masses, therefore all the


mathematics are invariant once the states are given. The energy levels are
still
E+ = E1 + E2 + 2J E = E1 + E2
but the difference is that the levels are not related to the exchange symmetries of the particles.

3.4

A helium-like system with non-identical particles

The exoticon-exoticon system (identical fermions) is indifferent with the


electron-electron system except for richer spin configurations for the two
symmetries. Yet no restriction upon symmetries of particle exchange is
placed on exoticon-electron system, therefore, the spatial orbitals can be
freely occupied by the two fermions, and for the fact that spin is not included
in the Hamiltonian, hence the energies levels are left unaltered.

3.5

Integrals in helium

Set a0 = 2Z, the integral in the curly brackets is


r2 e2r2 /2 e2r2 /4 + 1/4
and
J=

3.6

e2 5
Z = 34 eV
2a0 4

Calculation of integrals for 1s2p configuration


6

R
R10
20
R
21

Rnl

-10

r / a0

10

Figure 3: The plot of R10 , R20 and R21 with Z = 2.


The integral
J1s2p =

e2
0.00208 = 0.0283 eV
2a0
14

3.7

Expansion of 1/r12

Expansion in terms of spherical harmonics is the following




k
1
1 X r1 k 4 X
=
Ykq (1 , 1 )Ykq (2 , 2 )
r12
r2
r2
2k + 1
k=0

(3.8)

q=k

(a) Setting k = 0, 1, we have


1
1

{4/4
r12
r2

r1 4 3
+
(cos 1 cos 2 + sin 1 sin 2 cos(1 + 2 ))
r2 3 4


1
r1
=
1 + cos 12
r2
r2
(b) Mathematically, the expectation values of 1/r12 are always sandwiched
by bra-ket where the phase factors cancels; this is seen in the expression
for K1s nl . Physically, the quantum number m is responsible for magnetic
interactions but Coulomb repulsions have no interests in that.
(c) Due to the orthogonality relations of spherical harmonics, the terms
in 1/r12 are eliminated excluding the one with quantum numbers lm. For
l = 1, this corresponds to the second term in the expansion as shown in part
(a).
(d) This follows the arguments in part (c), the given l samples out the
order k in Eq (3.8).

The alkalis

4.1

Configuration of the electrons in francium


Fr = [Rn]7s1
Rn = [Xe]5d10 5f 14 6s2 6p6 6d10
Xe = 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 4f 14 5s2 5p6

4.2

Finding the series limit for sodium

Energy levels of sodium obey the rule


E=

Ry
13.6 eV
=
(n )2
(n )2
15

(4.1)

Then
E E 3/2

(E)2 E 3

The topmost level must have E = 0, and that energy corresponds ionization energy
which was found to be 5.1 eV. The effective principal number
p

n = 13.6/5.1 = 1.63.

4.3

Quantum defects of sodium

From formula Eq (4.1), the quantum defects are


3s 1.37

4s 1.34

5s 1.33

6s 1.35

the average quantum defect is 1.35 .02. Assume that the quantum defect
for 8s is still 1.35, the binding energy will be
ENa 8s = 13.6/(8 1.35)2 = 0.31 eV
while for hydrogen EH 8s = 0.21 eV.

4.4

Quantum defect

Quantum defect of Rb 5s is 3.19 with which that of 7s is approximated.


Therefore the energy difference reads


1
1
E = 13.6

= 3.22 eV
(5 3.19)2
(7 3.19)2
Then the wavelength of the two identical photons are
=

4.5

hc
= 771 nm
E/2

Application of quantum defects to helium and heliumlike ions

Throught a direct calculation, the wavelength from 1s3d to 1s2p is obtained as 625 nm, compared with 656 nm of hydrogen Balmer-.
Quantum defects can be evaluated by Eq (4.1), they are listed in Table
2. It is readily seen that s > p > d .
Table 2: Quantum defects of helium
1s2s
1s2p
1s3s
1s3p
1s3d
0.2356 0.0275 0.2265 0.0287 0.0026
To estimate binding energy of 1s4l states, assume the quantum defects
for l = 1, 2, 3, 4 as 0.23, 0.28, 0.0026, 0.00. Then the binding energies read
0.96, 0.98, 0.85, 0.85 eV
16

The second ionization energy of Li+ is


IE2 = (E E1s4f ) = 72.24 +

Z 2 Ry
= 75.64 eV
42

where Z = 2.

4.6

Quantum defects and fine structure of potassium

The wave numbers can be put into three groups (3 row vectors), and
take average and difference within each group. The data set becomes =
(hi , ). The energies are calculated through E = hc/, and the data
set for energies reads E = (hEi , E). Given that the ionization energy of
potassium IE = 4.34 eV, the energy levels are E IE from with we can find
out the effective principal quantum numbers and quantum defects. They
are n = 2.23, 3.26, 4.28 and l = 1.77, 1.73, 1.72; the pattern confirms that
they corresponds to 4p, 5p, 6p. The fine structure splitting E/E divided
by 2 are, for 4p, 5p, 6p, 49.18, 33.45, 26.38.
According to Lande formula,
Efs =

Zi2 Zo2
2 Ry
(n )3 l(l + 1)

(4.2)

the ratio of E/(n )3 should be 1:1:1 and it turns out to be 1.00 : 0.99 :
1.03. The transitions of 7p should produce spectral lines of wavelengths
321.84 nm, 321.93 nm.

4.7

The Z-scaling of fine structure

From Eq (4.2), fine structure splitting of ions scales as Z 4 , then for


it is 1.3 105 114 = 0.19 eV; for neutral ions it scales as Z 2 ,
namely, for sodium atom it should be 0.0016 eV.

Na+10 ,

4.8

Relative intensities of fine-structure components

(a) In this problem J = 1/2, 3/2, 5/2, hence the weight ratio should be
2 : 4 : 6 = 5 : 10 : 15 = 5 : (1 + 9) : (1 + 9 + 5).
(b) Possible electrical dipole transitions are D5/2 F5/2 , D5/2 D7/2 , D3/2
F5/2 with intensities 1 : 20 : 14.
Hint: Plot out energy levels and then count and take ratios.

4.9

Spherical symmetry of a full sub-shell

Show that
sum reads

Pl

m=l

|Ylm (, )|2 is spherically symmetric. For l = 1, the


s1 =

3
3
(cos2 + sin2 ) =
4
4
17

Associated Legendre polynomials are defined as follows


 m
d
Plm (x) = (1)m (1 x2 )m/2
Pl (x)
dx

(4.3)

and they are related to spherical harmonics in Eq (2.1).

The LS-coupling scheme

5.1

Description of the LS-coupling scheme

Central-field approximation is achieved by imposing spherical symmetry


on electron distributions where electrons are seated in several spherically
symmetric layers. The central field Hamiltonian is the sum of individual
electron Hamiltonian and hence the Shrodinger equations are decoupled.
The arrangements of pseudo-independent electrons constitute the electron
configurations. (a) The residual electrostatic interactions couples the electrons and give rise to splitting of energy levels. (b) Magnetic spin-orbit
interactions include another degree of freedom, the spin, which rotates the
original eigenstates resulting in further splittings.

5.2

Fine structure in the LS-coupling scheme

The spin-orbit Hamiltonian reads


hl1 Li
hs2 Si
hl2 Li
hs1 Si
S
+ 2
S
:= LS S L
S(S + 1)
L(L + 1)
S(S + 1)
L(L + 1)
(5.1)
3
For 3s4p P configuration, S = 1 = L, therefore the relation LS = 4p /2
holds if
2
1X
4p =
i hsi Si hli Li
2
Hso = 1

i=1

but consider the symmetry of electrons, the right hand side is just
X
i sik lik = 4p
i

5.3

The LS-coupling scheme and the interval rule in calcium

The ground configuration of calcium: 1s2 2s2 2p6 3s2 3p6 4s2 .
The triple lines comes from 3 P term with J = 0, 1, 2 with and interval
ratio 2. The first three of muiltiplet of six lines come term 3 DJ=1,2,3 with
an interval ratio 1.5; the rest must be 3 P, 3 D and 3 F from selection rules.

18

5.4

The LS-coupling scheme in zinc

The zero comes from 1 S0 , then it leaps to triplet 4s4p3 P0,1,2 , next it
jumps to singlet 4s4p1 P1 and 4s5s 3 S1 , 1 S0 .

5.5

The LS-coupling scheme

The interval rule accurately indicates that the four levels of Mg are 3 P0,1,2
and 1 P1 of 3s3p. Heavier Fe14+ shows a weaker interval pattern (2.4 rather
than 2) due to intercombination and therefore S 6= 0 transitions occurs in
Fe14+ but not Mg.

5.6

LS-coupling for configurations with equivalent electrons

(a) For np2 configuration (2 out of 6 states, 15-fold degenerate), ML =


ml1 + ml2 and MS = ms1 + ms2 , then ML = 2, 1, 0 and MS = 1, 0.
Considering Pauli exclusion, the 3 D and 3 S can be directly eliminated preserving 1 D (5-fold) and 1 S (1-fold). Then whats left is 15 5 1 = 9 and
3 P (9-fold) fits.
(b) The first 3 lines are the spin-orbit splittings of 3 P term, the latter
two are 1 D and 1 S. The weak emissions lines near 1 D indicates deviations
from LS-coupling scheme.
(c) In order to make MS = 2 and ML = 2 for six d-electrons, ms =
1 1 1 1 1
( 2 , 2 , 2 , 2 , 2 , 12 ) and ml = (2, {0}5 ) where curly bracket means all combinations. To meet Pauli exclusion principle and maximize MS , the longest
sequence of aligned ms is up to 5 since ld = 2, namely, five electrons are
equally spread out, therefore ms takes the form above and ML = ml (ms =
1
2 ) ld = 2.

5.7

Transition from LS- to jj-coupling

For configuration 3p4s, Hre > Hs-o due to a higher correlation energy (exchange integral) from inner core, while 3p7s is just the opposite, the electrons
seems more independent. Therefore, LS-coupling is proper for 3p4s and jjcoupling for 3p7s. The former gives two terms 3 P and 1 P while the latter
gives four levels: (3/2 = (1+1/2), 1/2)J=2 , (1/2 = (11/2), 1/2)J=1 , (1/2 =
(1 1/2), 1/2)J=0 , (3/2 = (1 + 1/2), 1/2)J=1 . It is shown in Figure 5.10
in the text.

5.8

Angular-momentum coupling schemes

Take the 0-2 and 1-1 difference of np(n + 1)s for n = 3, 4, 5, then take
their ratios, I find 02 /11 = 0.23, 0.70, 0.89. As n grows, the LS-coupling
transitions to jj-coupling, namely 02 /11 1.
The g-factor gJ = 1.06 should belong to 1 P (spin-0), the deviation from
1 is due to the mixing with other 3 P wavefunctions.
19

5.9

Selection rules in the LS-coupling scheme

(a) No, l = 2; (b) no, J = 2; (c) yes; (d) no, l = 0; (e) no, J = 2.
4d9 5s5p is the candidate that mixes with 4d10 5p.

5.10

The anomalous Zeeman effect

Electric dipole transition rules require MJ = 0, 1. The energy is


given by
EZM = gJ B BMJ
(5.2)
The transitions 3 S1 (gJ = 2)-3 P2 (gJ = 23 ) take place at MJ : [1, 0, 1]
[2, 1, 0, 1, 2], then (gJ MJ ) : [2, 0, 2] [3, 23 , 0, 32 , 3]. Therefore,
(gJ MJ ) = [(1, 32 , 2); ( 21 , 0, 12 ); (2, 23 , 1)] The spacing is B B/2 =
14 1/2 = 7 GHz with B = 1 T

5.11

The anomalous Zeeman effect

Formula for the g-factor:


gJ =

3 S(S + 1) L(L + 1)
+
2
2J(J + 1)

(5.3)

then gJ [ 3 S1 ] = 2 and gJ [ 3 P1 ] = 23 . Compared with the previous problem


(or Figure 5.13), since J = 0, MJ 6= 0, there are only six lines left.

5.12

The anomalous Zeeman effect

With previous experience and the fact J = 0 states have no Zeeman


splitting, possible transitions are:
3

P1 3 D2 (1),

P2 3 D1 (2)

and the g-factors are


3

P1 = 3/2

D1 = 1/2

P2 = 3/2
D2 = 7/6

The quantities
(gJ MJ )1 : [3/2, 0, 3/2] [7/3, 7/6, 0, 7/6, 7/3]
and
(gJ MJ )2 : [3, 3/2, 0, 3/2, 3] [1/2, 0, 1/2]
Therefore, 6(gJ MJ )1 = [+9, +7, +5; +2, 0, 2; 5, 7, 9] fits the data.

20

5.13

The anomalous Zeeman effect in alkalis

(a) gJ [( 2 S1/2 , 2 P1/2 , 2 P3/2 )] = (2, 2/3, 4/3)


(b) The g-factors are
gJ [3s 2 S1/2 ] = 2 gJ [3p 2 P3/2 ] = 4/3
It is a set of 2 to 4 transitions, then there are six lines. The intervals are
4/3[3/2, 1/2, 1/2, 3/2]2[1/2, 1/2] = [(5/3, 1)(1/3, 1/3)(1, 5/3)]
and they are equally spaced by 2/3 B B = 2/3 14 1 = 9.33 GHz
(c) There are only two lines of same intensity, no MJ = 0 transition.
(d) The energy of fine structure is 517.96 GHz this corresponds to a huge
magnetic field 517.96/9.33 = 55.5 T.

5.14

The Paschen-Back effect

Spin, in this case, is a spectator variable, then J = L, hence gJ =


3/2 1/2 = 1, same as in the normal Zeeman effect.

Hyperfine structure and isotope shift

6.1

The magnetic field in fine and hyperfine structure

The magnetic field is given by


2
B e = 0 gs B |ns (0)|2 s
3
where
|ns (0)|2 =

(6.1)

Z3
a30 n3

Setting Z = 1, s = 1/2 and n = 1, 2 for 1s and 2s, we have magnetic field


flux density at center as 16.7 T and 2.1 T respectively. The magnetic field
felt by an orbiting electron is B = l where is the spin-orbit interaction
constant given by Eq (2.7). Then the field that 2p-electron in hydrogen
experiences is 0.2 T.

6.2

Hyperfine structure of lithium

Hyperfine and fine structure splittings are both proportional to the magnetic moment (spin) and in turn, proportional to the mass. Therefore, hyperfine structure is of order me /Mp smaller than fine structure.
Let P = max{I, J} and Q = min{I, J}, then F = {P + Q, P + Q
1, . . . , P Q + 1, P Q} and hence there are 2Q + 1 values of F .
21

Since 2s has no fine structure, the fine structure totally comes from
2p 2 P3/2,1/2 with maximum J = 3/2 on the top. For 6 Li (at J = 3/2),
2I + 1 = 3, then I6 = 1 and for 7 Li, 2I + 1 = 4, I7 = 3/2, and notice both
are no larger than 3/2.
Interval Rule With computer, I find the splittings for I = 1 is 3 : 2 : 5,
the interval ratio is then 5 : 3; for I = 3/2, the splittings are 4.5 : 1.5 :
5.5 : 7.5 with interval ratio 3 : 2 : 1. The data confirms our prediction of
nuclear spins given the hyperfine constants for e to g negative.
The hyperfine shift of J = 1/2 level are 1 : 2 and 1.5 : 2.5, then the
gap ratio will be 3 : 4. From the 2s hyperfine structures, we can find out the
gI ratio of two isotopes, it is (228.2/803.5)(4/3) = 1/2.641. Then we have
X = 4 (26.1/3) 2.641 = 91.899 = 91.9 MHz

6.3

Hyperfine structure of light elements

The hyperfine structure can be estimated as


EHFS

Zi Zo2 me 2
Ry
(n )3 Mp

(6.2)

For ground state hydrogen, the hyperfine structure should be around 95 MHz
and for ground state lithium (Zi = 3, Zo = 1, n = 1.59), 71 MHz. Both
structures are badly underestimated.

6.4

Ratio of hyperfine splittings

For 1s state, J = 1/2, put in notation {element : I; F } we have relevant


quantum numbers for H, D and 3 He+ :
{H : 1/2; 1, 0}

{D : 1; 3/2, 1/2}

{3 He+ : 1/2; 1, 0}

Given A gI N Z 3 , gI I /I and interval rule, we have


EH /ED =

3/2 2.79
AH
=
= 4.3
3/2 AD
3/2 0.857

EH /E 3 He+ =

6.5

2.79
AH
= 0.16
=
A 3 He+
2.13 8

Interval for hyperfine structure

(a) The interaction can be expressed in terms of F, I, J,


EF = A hI J i =

A
{F (F + 1) I(I + 1) J(J + 1)}
2
22

(6.3)

Therefore, EF EF 1 = A2 {F (F + 1) F (F 1)} = AF , the interval rule.


(b) Apply the same method as the text demonstrated, F = 4.9, 6.1, 6.9, 8.1,
respectively for c, d, e, f. The nuclear spin is I = Fmax J = 811/2 = 5/2.
(c) From the peaks, it can be inferred that nuclear spin is 5/2 for both
isotopes, then A( 8 S7/2 ; 153) = 20 (4.86 2.35)/(6.42 0.77) = 8.9 MHz.

6.6

Interval for hyperfine structure

From the argument in (6.2), I postulate that 2I +1 = 6 and I = 5/2. The


splittings make the ratio 3.1 : 2.6 : 2.0 : 1.5 : 1.0 consistent with prediction
3.0 : 2.5 : 2.0 : 1.5 : 1.0.

6.7

Hyperfine structure

From the data: (a) 70/5 = 42/3 = 14, (b) 70/42 = 5/3, I conclude that
70 and 42 are two levels of 39 K and 5 and 3 the corresponding two levels
of 40 K. Since the intensities depend on degeneracies 2F + 1, then the two
levels are F = 1 and F = 2. Then nuclear spin is just I = 2 1/2 = 3/2,
consistent with the number of splittings (I > J). And the magnetic moment
(I = gI I, I the same) ratio (39 over 40) reads 1.6/(1.9 1.0) = 1.8.

6.8

Zeeman effect on HFS at all field strengths

(a) As B goes up, the atom moves from F - to J-scheme, and from
the numbers of splittings, we have 2J + 1 = 4, J = 3/2 and 2F1 + 1 =
5, 2F2 + 1 = 3, F = 2, 1. Hence I = 2 3/2 = 1/2.
(b) MJ is the good quantum number.
(c) The weak field Zeeman energy is
EZM, weak = gF B BMF

(6.4)

Same separations is equivalent to same gF which is


gF =

F (F + 1) + J(J + 1) I(I + 1)
hJ F i
gJ =
gJ
F (F + 1)
2F (F + 1)

(6.5)

J = 3/2, I = 1/2, F = 2, 1, from calculation the gF are different.


(d) The strong field Zeeman energy is
EZM, strong = gJ B BMJ + AMI MJ

(6.6)

If B B A, and J is same for both hyperfine states, then Zeeman splittings


are the same.
(e) The cross-over can be defined at B B = A = 3.4 GHz, or B =
3.4/14 = 0.24 T.

23

6.9

Isotope shift

The mass effect shifts the energy by

Mass

me A

Mp A A

(6.7)

while volume effect gives

Vol


2
rN
A Z 2

R
a20 A (n )3

(6.8)

and radius of nucleus is


rN 1.2 A1/3 fm

(6.9)

For rubidium isotopes A = 85 and A = 87, then total isotope shifts,


mass plus volume effects, read (a) .186 + .590 = .777 m1 (b) .202 + .590 =
.792 m1 .

6.10

Volume shift

From Eq (6.8), the relative uncertainty that rN contributes is


[
Vol ] = 2[rN ],

d[
Vol ] = 2%
Vol

For hydrogen 1s configuration, the volume shift is about 5 109 eV


1 MHz. Therefore, d[EVol ]/ELamb 1% 1/1057.8 1 ppm.

6.11

Isotope shift

Assume Z = A/2, n = 2, = 1/500 nm1 , then


A11/3 =

6.12

me
R /a30 32/(1.2 1015 )2
Mp

A = 71

Specific mass shift

P
Substitute the nucleus momentum for pN = N
i pi ,
ergy becomes


 N
N
X
me X 2
1
1+
pi pj
T =
pi + 2
2me
MN

i<j
i=1

{z
}
|
{z
}

| normal mass
effect

then kinetic en-

specific mass effect

24

6.13

Muonic atom

The radius is easily found to be


r=

n2 ~2
= a0 /2277
Zm e2

since n = 1, m = 207me and Z = 11. The muonic Bohr radius is way


much smaller than electronic Bohr radius. The binding energy is
En =

Z 2 e4 m
= 112 207 Ry/n2
2n2 ~2

If n = 1, E1 = 25047 Ry. Volume effect must be extremely evident since


the size of orbit is comparable to nucleus scale. Actually, it is about 4% of
the transition energy.

The interaction of atoms with radiation

7.1

Averaging over spatial orientations of the atom

(a) We need to show that | hxi |2 = | hri |2 /3.


Proof.
Z

d (cos sin ) =

d(cos ) (1 cos )

= y
4
=
3

1
y3
3

1
=
3

1 + cos(2)
2

2
2

d.

(b) Since there is no specific preference of coordinate system, the result


in (a) is valid for all three axes and hence any direction in space.

7.2

Rabi oscillations

(a) The proof is straightforward for equivalence of eqns 7.25 and 7.26.
The equation 7.26 allows for a family of solutions with arbitrary constant
phases, without loss of generality, set


||
Wt
c2 =
sin
= const (eiW t/2 eiW t/2 )
W
2
and plug it into the equation 7.26
2

c2 + i( 0 )c2 + c2 = 0
2
25

(7.1)

The first exponential gives


(W/2)2 ( 0 )W/2 + |/2|2 = 0
the second exponential (with minus sign) gives
(W/2)2 + ( 0 )W/2 |/2|2 = 0
Both cases are consistent, if 0 , with definition of W ,
W 2 = 2 + ( 0 )2

(7.2)

(b) The plot.


-2

10

12

14

1.2

1.2
F1
F2

0.8

0.8

0.6

0.6

0.4

0.4

0.2

0.2

-0.2

-0.2
-2

10

12

14

Figure 4: F1 for and F2 for 3

7.3

- and /2-pulses

(a) Try the ansatz c(t) = c exp(it/2), I find = , then with initial
conditions c(0) = [1, 0],
c1 (t) = cos(t/2)

c2 (2) = sin(t/2)

(b) A general solution takes the form,






t
t
|i = cos
+ |1i i sin
+ |2i
2
2
Initially,
|(0)i = cos |1i i sin |2i
26

(7.3)

Now set t = , then


|(t )i = sin |1i i cos |2i = i{cos |2i i sin |1i}
(c) Set t = 2, |(t2 )i = |(0)i.
(d) Set = 0 and t = /2,



(t/2 ) = (|1i i |2i)/ 2

(e) First set = 0, t = /2, then the state becomes


1 = {|1i i |2i ei }/ 2

with an orthogonal state


2 = {iei |1i + |2i}/ 2.

Here comes a second /2-pulse, the state evolves into


1 + ei
1 ei
|1i i
|2i
2
2

Therefore, the probabilities in |1i and |2iare sin2 (/2) and cos2 (/2).
(f )Since cos( + /4) = (cos sin )/ 2 and sin( + /4) = (cos +
sin )/ 2, then


1
1 i

U 2 =
2 i 1
Similarly,

and the phase shift in |2i

=
U

=
U



1 0
0 ei


0 i
i 0

Then the successive operator reads


U
U

=U
U
U
2
 2
cos 2
= ei/2
sin 2

7.4

sin 2
cos 2

The steady-state excitation rate with radiative broadening

(a) The differential equation reads c2 = 2 c2 , the solution reads, from


inspection, c2 (t) = c2 (0)et/2 .

27

(b) Since

integration gives

d  t/2 

= ic1 ei(0 +i/2)t


c2 e
dt
2
c2 (et/2 1) = i

ei(0 +i/2)t
2 /2 i( 0 )

where c1 = 1 in the weak excitation. In the limit t 1,


|c2 |2 =

7.5

2 /4
( 0 )2 + 2 /4

Saturation of absorption

(a) Transmission in a weak resonant field takes the simple form


I(, z) = I(, 0)e()z = I(, 0)eN ()z

(7.4)

For transmission 1/e, N = 1. The absorption cross-section reads


() =

g2 2 c2
A21 gH ()
g1 02

(7.5)

where g1 , g2 are the degeneracies of two states and gH is the Lorentzian line
shape function

1
(7.6)
gH () =
2 ( 0 )2 + 2 /4
For a simple two level system ( = A21 ) with g2 /g1 = 3 at resonance,
(0 ) = 3

2c2 A21
320
=
2
02

(7.7)

Sodium s-p transition has 0 = 589 nm, invoking Eq (7.7), we have


N = 6 1012 .
(b) The saturation intensity is defined as
Is () =

~A21
2()

(7.8)

and the fact that Isat = Is (0 ), Isat /Is = 0 (0 )/(). The absorption
coefficient is defined
N ()
(, I) =
(7.9)
1 + I/Is ()
then we can find (, Isat ). Notice = 1/ = 6 ns for sodium at = 589 nm.

28

7.6

The properties of some transitions in hydrogen

(b) The A21 for 3s, 3p and 3d are 6.3 106 s1 , (17 + 2.2) 107 s1 and
6.5 107 s1 , the lifetimes = 1/A21 are then 160, 5.5, 15 ns.
(c) Shorter lifetime means larger spontaneous transition rate. Since 1s2p overlaps much more than 1s-3p, transition rate is higher for the former
and hence shorter lifetime.
(d) The Einstein coefficients satisfy the following relations
A21 =

~ 3
B21
2 c3

g1 B12 = g2 B21

(7.10)

and radial matrix element D12 is contained in


B12 =

e2 |D12 |2
30 ~2

A21 =

g1 4 3
|D12 |2
g2 3c2

(7.11)

Then the D12 s for transitions 2p-3s, 1s-3p, 2s-3p, 2p-3d and 1s-2p are
0.53, 0.52, 3.0, 3.8, 1.3, measured in a0 .
(e) The saturation intensity is given by
Isat =

hc
hc
=
3 3
3 3

(7.12)

For the case where spin and fine structures are ignored, = A21 .
Now calculate the saturation intensities for 2p-3s and 1s-3p. The A21 are
(6.3 106 , 1.7 108 ) s1 , the wavelengths are 1./R (5/36, 8/9), therefore
Isat = (0.46, 3.7 103 ) mW/cm2 .

7.7

The classical model of atomic absorption

The dynamical equation takes the form


x
+ x + 02 x =

F (t)
cos t
m

(7.13)

The steady state ansatz takes the general form x(t) = Aei(t+) and plug
it into the dynamical equation (I have secretly replaced cos t by eit ), we
have
F (t) i
e
2 + i + 02 =
mA
(a) Take the real part of the ansatz,
x = A cos(t + )
= A(cos t cos sin t sin )

: = u cos t v sin t

29

(b) Notice that


p

u2 + v 2 = A


F0 /m ei


= 2
2 + i
0

=p

F0 /m

02 )2 + ()2

1/2
2
F0
2
( 0 ) +

2m
4
( 2

The peak is located at 2 = 02 2 /2.


(c) The phase is given by
tan =
=

v
u
2

02

The first line comes from (a) and the second line comes from the complex
algebraic equation above.
(d) Combine (b) and (c).
(e) Notice that P |A|2 and simply invoke (b) we have,
P

7.8

1
( 0

)2

+ (/2)2

Oscillator strength

(a) Integrate the cross-section in Eq (7.5) gives


Z


g2 2 c2 g1 4
()d =
|D12 |2 3
2
2
g1 0 g2 3c

2 c2 4
|D12 |2 03
2
0 3c2
= 2 2 r0 cf12
where, as you may check, r0 = ~/me c = 2.8 1015 . Note, I computed
the complicated integral with computer algebra system and made approximations by hand.
(b) The cross-section can be calculated from
() =

P ()
8/c
e4 4
=
2
2
2
3
(c/8)E0
3m3 c ( 02 )2 + 2 2

30

(c) For an harmonic oscillator E = K + U = 2K, if we assume that


oscillation is much faster than the damping, then this formula holds and we
have


E = m x 2 = mx20 et 4 cos2 ( t) = mx20 et 4 /2

Then, according to the classical damping formula (1.23), the damping rate
is
E
e2 2
1
= ==

E
60 me c3
(d) Combine the result in (b) and (c).
(e) From Eq (7.11), we have
|D12 |2 =

g2 33
A21
g1 4c(2)3

(7.14)

and for sodium 3s-3p transition, A21 = 2 107 s1 , = 589 nm, therefore
|D21 |2 = 5.3 1020 C2 m2 . Absorption oscillator strength is, by definition,
2
f12 = 2me 0 D12
/(3~) = 0.980

(7.15)

(f ) For hydrogen 1s-2p and 1s-3p the oscillator strengths follow from the
formula
3 mc2 A21
f12 =
2 ~ 2
and they are 0.418, 0.0801.

7.9

Doppler broadening

In the rest frame and moving frame the frequency differs by = 0 =


kv. And the sinc2 behaves like a delta, then v = (0 )/k in f (v).

7.10

An example of the use of Fourier transforms

I recommend first complexify the expression, then apply Fourier transform and finally take the real part. It is straightforward if you look it up in
the table and the final result will be a Lorentzian with peak at .

7.11

The balance between absorption and spontaneous emission

It comes from the Einstein equation


N 2 = (N1 B12 N2 B21 )(12 ) N2 A21

(7.16)

at equilibrium and if we neglect the contribution from spontaneous emission,


the absorption is
I = (N1 B12 N2 B21 )(12 )~ = N2 A21 ~
31

Note that N2 = N 22 and substitute eqn (7.69) for 22 , then we have eqn
(7.87) invoking the definition
I
Isat

7.12

22
2

(7.17)

The d.c. Stark effect

(a) The perturbation is similar to intermediate field strength in the


discussion of Zeeman effect. The eigenvalues are
1,2 =

V2
)
V 2 + 2 /4 ( +
2

(b) See part (a).


(c) For 3s-3p transition, = hc/ = 2.11 eVThe displacement will be
of the order a0 , then the electrostatic energy will be of the order V =
eE0 a20 /2 1018 eV. Then E = V 2 / 1037 eV.

32