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
=
5R mH
mD
18me
= 0.18 nm
5mH R
H D =
where mD 2mH .
1.2
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
E
4
=
= 2 = 75076
= (ch/E) (dE/E)
= (dE/E)
(1.13)
1.4
Xrays
1.5
f Z
Xrays
1.6
Xray experiments
See http://www.physics.ox.ac.uk/
history.asp?page=Exhibit10
1.7
2
E = E/75076 = 0.3 eV
n2
1.8
E
= 4.5 104 %
E
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.
1.9
Blackbody radiation
1.10
Zeeman effect
1.11
1.12
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
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).
Key formulas
Ylm (, ) = (1)m
Z
(2l + 1) (l m)! im m
e Pl (cos )
4(l + m)!
(2.1)
Z
d sin m cos n = 0
(2.2)
(2.3)
(2.4)
d =
sin d =
d(cos )
1 2
1
2
sin
+
L =
sin
sin2 2
Eso = hS Li =
2.1
(2.5)
(2.6)
(2.7)
(2.8)
Angularmomentum eigenfunctions
cos d(cos ) = 0
1
2.2
Angularmomentum 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
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)
2.4
Hydrogen
rb
0
:= ab
y 2 dy 2y
e
0
3 e2 / (rb /a0 )3
2.5
e(1 rb /a0 )
a30
=
= 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
100 nm
Infrared 1000 nm
2.7
0.45 ns
450 ns
Selection rules
2.8
Spinorbit interaction
l
2
Ej = (l + 1)
2
2.9
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 + 2AB1 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
(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 zaxis.
(e) The case of (a) is akin to the vertical motion of the electron while (d)
corresponds to righthanded 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
(2.11)
Then we write
( + i cot ) (eim ) = 0
it is equivalent to
cos
=m
sin
2.12
If l1 l2 is even, then
Iang = (1)l1 l2 +1 Iang = Iang
which implies the integral vanishes.
To have nonvanishing 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
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
e2
e2
Zm
e4
=
r12
rm
~2
3.2
(3.4)
(3.5)
Ai =
hA H
Note that
(3.6)
(3.7)
H = H
H = H
Ai = H H = J K
hA H
(1 1 + h  i c.c)
= Im h  i
2
3.3
~2 2
2m x
u1 = (2/l)2 u1 ,
~2 2
2ml2
E1 =
12
2~2 2
ml2
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 notouch, 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 0spin, and the antisymmetric spatial functions should have
spin1 or spin0 but they do not exist.
13
3.4
3.5
Integrals in helium
3.6
e2 5
Z = 34 eV
2a0 4
R
R10
20
R
21
Rnl
10
r / a0
10
e2
0.00208 = 0.0283 eV
2a0
14
3.7
Expansion of 1/r12
(3.8)
q=k
{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 braket 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
4.2
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
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
= 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
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
Z 2 Ry
= 75.64 eV
42
where Z = 2.
4.6
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
Na+10 ,
4.8
(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
Show that
sum reads
Pl
m=l
3
3
(cos2 + sin2 ) =
4
4
17
(4.3)
5.1
5.2
i=1
but consider the symmetry of electrons, the right hand side is just
X
i sik lik = 4p
i
5.3
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 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 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
5.7
For configuration 3p4s, Hre > Hso due to a higher correlation energy (exchange integral) from inner core, while 3p7s is just the opposite, the electrons
seems more independent. Therefore, LScoupling 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
Take the 02 and 11 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 LScoupling
transitions to jjcoupling, namely 02 /11 1.
The gfactor gJ = 1.06 should belong to 1 P (spin0), the deviation from
1 is due to the mixing with other 3 P wavefunctions.
19
5.9
(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
5.11
3 S(S + 1) L(L + 1)
+
2
2J(J + 1)
(5.3)
5.12
P1 3 D2 (1),
P2 3 D1 (2)
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
5.14
6.1
(6.1)
Z3
a30 n3
6.2
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
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
{D : 1; 3/2, 1/2}
{3 He+ : 1/2; 1, 0}
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
A
{F (F + 1) I(I + 1) J(J + 1)}
2
22
(6.3)
6.6
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
(a) As B goes up, the atom moves from F  to Jscheme, 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)
F (F + 1) + J(J + 1) I(I + 1)
hJ F i
gJ =
gJ
F (F + 1)
2F (F + 1)
(6.5)
(6.6)
23
6.9
Isotope shift
Mass
me A
Mp A A
(6.7)
Vol
2
rN
A Z 2
R
a20 A (n )3
(6.8)
(6.9)
6.10
Volume shift
d[
Vol ] = 2%
Vol
6.11
Isotope shift
6.12
me
R /a30 32/(1.2 1015 )2
Mp
A = 71
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
24
6.13
Muonic atom
n2 ~2
= a0 /2277
Zm e2
Z 2 e4 m
= 112 207 Ry/n2
2n2 ~2
7.1
d (cos sin ) =
d(cos ) (1 cos )
= y
4
=
3
1
y3
3
1
=
3
1 + cos(2)
2
2
2
d.
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)
(7.2)
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
7.3
 and /2pulses
(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)
(7.3)
(t/2 ) = (1i i 2i)/ 2
1 = {1i i 2i ei }/ 2
2 = {iei 1i + 2i}/ 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,
=
U
=
U
1 0
0 ei
0 i
i 0
=U
U
U
2
2
cos 2
= ei/2
sin 2
7.4
sin 2
cos 2
27
(b) Since
integration gives
d t/2
ei(0 +i/2)t
2 /2 i( 0 )
7.5
2 /4
( 0 )2 + 2 /4
Saturation of absorption
(7.4)
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)
~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
(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 1s3p, 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)
e2 D12 2
30 ~2
A21 =
g1 4 3
D12 2
g2 3c2
(7.11)
Then the D12 s for transitions 2p3s, 1s3p, 2s3p, 2p3d and 1s2p 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 2p3s and 1s3p. 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
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
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
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 A2 and simply invoke (b) we have,
P
7.8
1
( 0
)2
+ (/2)2
Oscillator strength
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 crosssection can be calculated from
() =
P ()
8/c
e4 4
=
2
2
2
3
(c/8)E0
3m3 c ( 02 )2 + 2 2
30
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 3s3p 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 1s2p and 1s3p the oscillator strengths follow from the
formula
3 mc2 A21
f12 =
2 ~ 2
and they are 0.418, 0.0801.
7.9
Doppler broadening
7.10
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
(7.16)
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)
V2
)
V 2 + 2 /4 ( +
2
32
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