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Lecture 12: Time-Dependent Perturbation Theory: Emission and Absorption of Radiation (10/27/2005)
Lecture 12: Time-Dependent Perturbation Theory: Emission and Absorption of Radiation (10/27/2005)
rate of stimulated emission. You can see that this rate is proportional to the
energy density of radiation per unit frequency (its density both in space
as well as in the spectrum of energies). This proportionality is what we have
seen: the probabilities were proportional to |Vba |2 and the energy density will
also be proportional to the squared perturbations the squared electric field,
for example. Once again, Bba (ba ) is the rate of stimulated emission
|bi |n
hi |ai |(n + 1)
hi.
In the very same way, Bab (ba ) is the rate of stimulated absorption:
|ai |n
hi |bi |(n 1)
hi.
Note that there cant be any spontaneous absorption if there is nothing to
absorb. Finally, we are getting to an equation. The atoms are in equilibrium
which implies
0=
dNb
= Nb A Nb Bba (ba ) + Na Bab (ba ).
dt
(ba ) =
A
eh/kT Bab
Bba
Another thing he had to figure out was that Bab = Bba . It follows from
Plancks formula (derived at the beginning of the course)
h
3
() = 2 3 h/kT
c (e
1)
because the ratios of the two terms agree for both denominators if Bab = Bba .
Finally, by matching the two equations for (), we may see that Einsteins
A, B coefficients are
Bab = Bba ,
A=
3
h
ba
Bba .
2 c3
Calculating Bba
We want to calculate Bba , the coefficient of the stimulated emission, for the
case of thermal environment with isotropic, uniform, incoherent, and unpolarized photons. More precisely, we want to calculate the leading contribution to Bba . Despite our goal, we must start with a monochromatic, linearly
polarized electromagnetic wave
~ r , t) = E0 cos(~k ~r t)
E(~
~ r , t) = E0 k cos(~k ~r t)
B(~
c
where is the frequency, k = c is the momentum, k is its direction (unit
vector), and is the polarization direction (for the electric field). Draw
a simple figure. How does this field act on charged particles? Recall the
Lorentz force law
F~ = e(E + ~v B)
which means that the magnetic force will be v/c times the electric force.
Recall that e < 0 for electrons. In physics of atoms we consider, |v/c| 1,
which is why we may use non-relativistic physics and neglect the magnetic
force. Positively speaking, we only want to consider the first-order effect of
the electric field.
The wavelength of the relevant electromagnetic waves we consider
=
2
k
will usually be longer than 100 nm which is much more than 0.1 nm, the
typical size of the atom. This allows us to assume that the electric field is
uniform over the atom. If we locate the (nucleus of the) atom at ~r = 0, the
previous formula for the electric field becomes
~ r , t) = E0 cos(~k ~r t) = E0 cos(t)
E(~
The Lorentz force is then simply
F~ = eE0 cos(t).
It may also be written in terms of the potential energy:
~
F~ = V
V = eE~ ~r
~
Vba = E~ P.
3
For a given electric field, this can be plugged as the time-dependent perturbation of the Hamiltonian into the calculations from the previous lecture.
Because
~ 2
E~ = |E0| |Vba |2 = E02 |
P|
and our first-order perturbative calculations give us
Pba
2
E02
2 sin [(ba )t/2]
~
P|
= 2 |
(ba )2
h
Averaging
So far we considered a monochromatic, linearly polarized wave moving in a
specific direction. But we want to know how the atom responds to wideband, unpolarized, isotropic radiation because only in this case Einsteins
formula applies as originally written down. In other words, we must try to
average over directions, frequencies, polarizations, and so forth.
Let us start with the frequencies. The time-averaged energy density is
R
()d, the integrated contribution from all frequencies; and we eventually
want to write our results using (). But the time-averaged energy density
may also be written as the time average of
1
1 2
= 0 E 2 +
B .
2
20
The electric and magnetic components contribute the same amount. Therefore, we need the average of 0 E 2 . For an oscillating E, it is simply
1
0 E 2 =
2 0
()d
where the factor 1/2 appeared as the time-average of cos2 (t). The averaging of our probability formula over time and frequencies may therefore be
obtained by replacing E02 according to the identity above, leading us to
Pba
~ 2Z
sin2 [(ba )t/2]
2|
P|
()
=
d
(ba )2
0
0h
2
Let us now assume that () does not depend on too much; it is slowly
varying. Only the frequencies near = ba will contribute significantly, as
we will see again, so you just require () to be slowly varying in this region.
Not a big assumption. But it allows you to replace () by (ba ) which
means
Z
~ 2
2|
P|
sin2 [(ba )t/2]
Pba =
(
)
d
ba
(ba )2
0
0 h
2
The integral may be calculated easily. Let us switch our variables
x=
( ba )t
2
2
d = dx
t
4
and slightly extend the limits for x to (, ) (this wont bring any factor
of two because x could have both signs anyway). We get:
Pba
Z
~ 2
|
P|
sin2 x
dx
(
)t
ba
x2
0 h
2
The integral over x equals as you can see using the residue techniques if
you wish. Replace the integral by and the rate i.e. the probability per unit
time is obtained from the previous formula by omitting t:
Rba =
~ 2 (ba ).
|
P|
0 h
2
We also need to average over , more precisely over the relative orientation
~ which is random. Note that
between and P
~ 2 = |
~ 2 cos2 ,
|
P|
|2 |P|
and
2
hcos i =
|
| = 1
+1 2
z dz
d cos2
1
R
= 1
=
R +1
d
3
1 dz
With this result, the rate (probability per unit time) of transition for unpolarized, incoherent, isotropic radiation is given by
Rba =
~ 2
2 |P| (ba ).
30h
This formula is a special example of Fermis golden rule we will discuss later.
Recall that this quantity is what we used to call Bba (ba ) which implies
Bba =
~ 2 = Bab ,
|P|
30h
2
A=
3
3 ~ 2
h
ba
ba
|P|
B
=
ba
2
3
c
30 h
c3
dNb = Nb A dt
For a single atom that started as |bi, you may also say that the probabilities
will go like
Pb (t) = exp(At),
Pa (t) = 1 exp(At).
Pb (t) = exp(t/ ).
5
Akn
1
.
n Akn
=P
Here we must really sum these three terms. If you have a feeling that this
is like taking three times the squared dipole because only the dipole in the
direction relevant for a particular wave should be included, recall that we
have already included the factor 1/3 from the averaging over the angles, and
therefore our full formula agrees with your intuition. We may also express
the squared dipole using the spherical tensors
m=q
Tq k = Yl=k
(~r).
In terms of the components, the relevant ones have k = l = 1 and they are
T+11 = 12 (x + iy)
T01 = z
T11 = + 12 (x iy)
x = 12 (T11 T+11 )
y = i2 (T11 + T+11 )
z = T 1
0
Inserting these formulae for x, y, z into our formula for the dipole, we obtain
1
1
|hb|(T11 T+11 )|ai|2 + |hb|(T11 + T+11 )|ai|2 + |hb|T01 |ai|2
2
2
h
i
2
1
2
1
2
= e |hb|T1 |ai| + |hb|T0 |ai| + |hb|T+11 |ai|2
~ 2 = e2
|P|
Selection rules
We want to identify some necessary assumptions for the transition to occur.
Recall that the Wigner-Eckart theorem implies that
0
2l + 1
6
or l = l0 1) and (m = m0
or m = m0 1)
Parity
There is one more selection rule due to parity. It is the operator defined by
r)i = |(~r)i.
|(~
The operator squares to one which also means that its eigenvalues must be
1. Its commutation properties with ~r, ~p are given by
r = ~r
~
p = ~p
~r} = 0
{,
~p} = 0
{,
where the second line follows from the first since ~p = d~r/dt. However, two
minus signs cancel for
~ = ~r p~,
L
L
~ = +L
~
L]
~ = 0.
[,
Lz , L2 ,
all commute with each other, we can simultaneously
Because H,
diagonalize all of them. This also means that the spherical harmonics must
acts as
be eigenvalues of the parity operator. In spherical coordinates,
:
and by looking at the form of the functions, you will see that
m = (1)l Y m .
Y
l
l
Because parity is a hermitian operator,
ha|bi = 0
if |ai, |bi have different parity. The proof is simple,
= a ha|bi = b ha|bi = 0
ha||bi
for a 6= b .
7
or m = m0 1)
(magnetic dipole)
(electric quadrupole)
m = 0, 1,
l = l0 = 0 forbidden
m = 0, 1, 2,
l = l0 = 0 forbidden