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Introduction
With the usual Hamiltonian for the hydrogen-like atom (in the Gaussian
unit),
p~2
Ze2
H0 =
,
(1)
2m
r
we have the n2 -fold degeneracy of states with the same principal quantum
number, or 2n2 -fold once the spin degrees of freedom is included. In the real
world, however, the degeneracy is lifted by corrections that arise due to the
special relativity. Note also that m in the Hamiltonian is not the mass of
the electron, but the reduced mass m = (me mp )/(me + mp ) which is smaller
than the electron mass by about 0.05%.
It is useful to recall that the electron in the hydrogen atom is nonrelativistic, v c, but not that slow. The expectation value of the kinetic
energy for the state |nlmi is
hnlm|
1
Ze2
(Ze2 )2 m
p~2
= Z 2 2 (mc2 ).
|nlmi =
=
2
2m
2a0
2
2
h
(2)
Big-Bang cosmology by comparing the calculation of light element abundances to the observation. See, e.g., http://astron.berkeley.edu/mwhite/
darkmatter/bbn.html by our own Martin White.
Fine Structure
The fine structure of the hydrogen atom refers to the (Z)2 correction to the
energy levels. It consists of three perturbation Hamiltonians. The first one
is the relativistic correction
Hrc =
(~p2 )2
,
8m3 c2
(3)
m2 c4 + p~2 c2 = mc2 +
p~2
(~p2 )2
+ O(p6 ).
2m 8m3 c2
(4)
1 1 dVc ~ ~
(L S).
4m2e c2 r dr
(5)
Of course the central potential is Vc = Ze2 /r for the hydrogen atom, but it is
left general so that it is applicable to multi-electron atoms as we will discuss
in 221B. The Coulomb field of the proton (or nucleus) appears partially as a
magnetic field in the moving reference frame of the electron, and the magnetic
e ~
~ However, this argument suggests
moment of the electron ~ = 2mc
(L + g S).
twice as large contribution, as discussed in Sakurai, p. 305.
When Goudsmit and Uhlenbeck suggested the electron spin, apparently
Heisenberg wrote to them immediately asking what they have done with a
factor of two. They didnt think they could calculate the spin-orbit correction, and they hadnt. If they had, they may not have had courage to
publish it, according to Goudsmits reminiscence at http://www.lorentz.
leidenuniv.nl/history/spin/goudsmit.html. L.H. Thomas, in his paper
Nature 107, 514 (1926), pointed out that this naive calculation is incorrect.
Because is the electron goes around the nucleus, and namely has a constant
acceleration, the native Lorentz transformation of the electric field to the
magnetic field does not give the right answer. One has to set up the reference frame that is always parallel to each other, which inevitably rotates
2
around in the electron rest frame. The Story of Spin by Sin-itiro Tomonaga has a detailed account on this point. At the end of the day, Thomas
showed that the spin-orbit coupling is a factor of two smaller than the naive
expectation, leading to the above Hamiltonian.
The third and the last one is the so-called Darwin term,
HDarwin
h
2
Vc .
=
8m2e c2
(6)
h
2
4Ze2 (~x)
8m2e c2
(7)
because 1r = 4(~r). The origin of this term is more subtle than the
previous two terms.
The relativistic wave equation was written down by Dirac, which we will
discuss in 221B. It predicted the existence of anti-matter, namely positron
for the electron and anti-proton for the proton, which were discovered later
by Caltech group (positron) and Berkeley group (anti-proton). At the same
time, it was a fully relativistic theory that predicts both the relativistic correction and the spin-orbit coupling automatically without resorting to any
arguments. They just come out from the equation. In addition, the wave
equation predicts that the relativistic electron doesnt sit quietly. It undergoes a frantic back-and-forth motion which Schrodinger named Zitterbewegung, a German word made of jitter and motion. The position of the
electron is smeared due to this motion by a distance of so-called the Compton wavelength h
/me c ' 4 1011 cm. Therefore the potential energy the
electron experiences is not strictly at a particular position, but rather an
average around that point. The correction can be computed in a Taylor
expansion around the average position r0 ,
~ i
~ j Vc (r0 ),
~ c (r0 ) + 1 h(ri )(rj )i
Vc (r) = Vc (r0 ) + h(~r)i V
2!
(8)
and the spherical symmetry of Zitterbewegung says hri i = 0, and h(ri )(rj )i =
2
( 4mh2 c2 )2 ij . This argument leads to the Darwin term above. Again, the Dirac
e
theory leads to this term automatically as we will see in 221B.
3
The first-order energy shifts due to these perturbations are simply expectation values with respect to the unperturbed states. The only tricky aspect
is that the unperturbed states are degenerate. However, it is easy to see that
the spin-orbit coupling is diagonal in the eigenstates of the total angular momentum J~2 |njlmj i = j(j + 1)h2 |njlmj i and Jz |njlmj i = h
mj |njlmj i, and
this is the basis we use.
First with the relativistic correction. Using the unperturbed Hamiltonian,
Ze2
Ze2
p~2
|njlmj i = 2 +
|njlmj i,
2m
2n a
r
!
(9)
we can rewrite
Ze2
Ze2
1
hnjlm
|
+
hnjlmj |Hrc |njlmj i =
j
2mc2
2n2 a
r
(Ze2 )2
1 1
1
1
=
2
+ 2
2
4
2
2mc
4n a
na r
r
!
(Ze2 )2
1 1
1
1
=
+
2mc2 4n4 a2 n2 a n2 a n3 a2 (l + 12 )
(Ze2 )2 1
=
2mc2 4n4 a2
(Z)4 mc2
=
8n4
!2
|njlmj i
4n
3
l + 12
!
4n
3
l + 12
3
(Z)4 mc2 4n
j
=
4n
4
8n
3
j+1
(j = l + 12 )
(j = l 12 )
(10)
(11)
2
j 32 |njlmj i
(j = l 21 )
4
1 Ze2 ~ ~
(L S),
2m2e c2 r3
(12)
and hence
Ze2 h
2
hnjlmj |HLS |njlmj i =
2m2e c2 2
j 21
1
j 3
r3
2
(j = l + 12 )
(j = l 21 )
(13)
It is known that
1
r3
1
1
3
3
a n l(l + 12 )(l + 1)
(14)
Ze2 h
2
hHLS i =
2m2e c2 2n3 a3
(Z)4 mc2 1
=
4
n3
1
j(j+ 12 )
1
(j+ 12 )(j+1)
(j = l + 12 )
(j = l 12 )
1
j(j+ 21 )
1
(j+ 12 )(j+1)
(j = l + 12 )
(j = l 12 )
(15)
The Darwin term has an expectation value only for the s-states, because
(r) rl .
h
2
4Ze2 |(0)|2 ,
(16)
hHDarwin i =
8m2e c2
Using (A.6.3) in Sakurai,
Rn0 (r) =
(
2
na
3
(n 1)!
2n[n!]3
d
L (),
d n
)1/2
(17)
Lp () = p! p!p + O(2 ),
(18)
(19)
and hence
Rn0 (0)Y00
and hence
|(0)|2 =
3
(
2
na
3
(n 1)!
2n[n!]3
)1/2
(n!n)
1
,
4
(20)
(n 1)!
1 4
1
=
(n!n)2
.
3
2n[n!]
4
4 n3
(21)
h
2
(Z)2 mc2
2 1 4
4Ze
=
.
8m2e c2
4 n3
2n3
(22)
2
na
Due to some reason, this expression coincides with that of the spin-orbit
coupling when l = 0, j = 1/2.
Finally, we put them together:
hHrc + HLS + HDarwin i
3
2
4
(Z)4 mc2 j + n + j(j+ 12 )
=
4
2
j+1
+ n3 (j+ 1 )(j+1)
8n3
2
(j = l + 21 )
(j = l 21 )
(Z)4 mc2
8n
=
3
.
4
8n
2j + 1
!
(23)
En,j = mc2 1 +
nj
1
2
2 1/2
q
,
+ (j + 21 )2 (Z)2
(24)
(25)
Hyperfine Interaction
~ B
~ = 1E
~ + 4 ~,
c
c
1
~ E
~ = B,
~
c
~ B
~ = 0.
(26)
(27)
(28)
(29)
1 ~ 2 ~ 2
1~
dtd x
E B + A ~ .
8
c
3
(30)
1~
1 ~ 2 ~ 2
~
dtd x
E B + A ~ + ~ B(~x ~y ) ,
8
c
3
(31)
where ~y is the position of the magnetic moment. The equation of motion for
~
the vector potential is obtained by varying the action with respect to A,
~ B
~ = 1E
~ + 4 ~ 4 (~
~ x ~y ).
c
c
(32)
(33)
(34)
~ f
~ where f is a scalar
but this misses possible terms of the form B
function.
To solve it, we use Coulomb gauge and write Eq. (33) as
~ = 4 (~
~ x ~y ).
A
(35)
1
Because |~x~
= 4(~x ~y ), we find
y|
~ x) =
~
A(~
~x ~y
1
= ~
.
|~x ~y |
|~x ~y |2
(36)
1
1
~ )
~
+ (~
.
|~x ~y |
|~x ~y |
(37)
"
~ x) = 8 ~(~x ~y ) + 1 3 ~r ~ ~r ~ ,
B(~
3
r3 r r
(39)
"
~ x) = 8 ~1 ~2 (~x ~y ) 1 3 ~1 ~r ~2 ~r ~1 ~2 . (40)
H = ~1 B(~
3
r3
r
r
In the MKSA system, it is
~ x) = 20 ~1 ~2 (~x ~y ) 0 1 3 ~1 ~r ~2 ~r ~1 ~2 . (41)
H = ~1 B(~
3
4 r3
r
r
8
e
~se ,
2me
~p = gp
|e|
~sp ,
2mp
(42)
|e|
h
2me
and N =
|e|
h
,
2mp
(43)
20
4
2.79N e 2 (~sp ~se )(~x).
3
h
(44)
The first order perturbation of this Hamiltonian gives the hyperfine splitting
Ehf = +
with |(0)|2 =
operators are
20
4
2.79N e 2 (~sp ~se )|(0)|2 ,
3
h
(45)
a3
0 for the 1s state. Finally, the eigenvalues of the spin
1
~sp ~se = ((~sp + ~se )2 ~s2p ~s2e ) =
2
2
h
4
2
3h4
(F = 1)
(F = 0)
(46)
3
4
4
a30
h
20
4
20
e
h e
h 4
=
2.79N e 3 =
2.79
= 9.39 1025 J. (47)
3
a0
3
2me 2mp a30
!
Parametrically, it is 2 (me /mp ) times the binding energy, and hence even
more suppressed than the fine structure.
The cosmic thermal bath has T = 2.7 K and hence kT = 3.7 1023 J,
which is much larger than the hyperfine splitting.
Radio Astronomy
10
Figure 1: Emission of the 21cm line from a spiral galaxy. Taken from hepph/9712538.
11
Figure 2: The rotation curve of a spiral galaxy. The dashed line labeled
disk is the prediction of the rotation speed if the stars in the disk are
the only source of gravity to hold the galaxy together. Clearly the disk
contribution is not enough. The so-called halo of the galaxy which is not
made of stars is holding the galaxy together. It shows the evidence for Dark
Matter that makes up the galactic halos. Taken from hep-ph/9712538.
12