Radiative and non-radiative transitions

Radiative
boundbound
absorption
spontaneous emission
stimulated emission
boundfree: photoionization
freebound: radiative recombination
fluorescence / Auger effect
Collisional
excitation
deexcitation
collisional ionization/recombination
Piotr ycki; PhD Course Astrophysical spectroscopy , CAMK, 2007, http://www.camk.edu.pl/~ptz/wyklad.html
Reminder energy levels
Hydrogen
Radiative transitions
Bound bound transitions: Einstein coefficients
1. Spontaneous emission
A
ul
= transition probability per unit time for spontaneous emission (sec
-1
)
2. Absorption
B
lu
J = transition probability per unit time for absorption
- line profile
3. Stimulated emission
B
ul
J = transition probability per unit time for stimulated emission
Relations between Einstein coefficients:
(transitions between levels 1 and 2 have to balance)
g
l
, g
u
statistical weights of the levels involved,
e.g.,

J
+
(+)d +;

0

(+) d +=1
g
l
B
lu
=g
u
B
ul
A
ul
=
2 h+
3
c
2
B
ul
g=2 J +1
Einstein coefficients
Quantum mechanical calculations of transition probabilities
w
if
=
4n
2
e
2
m
2
c
J (o
if
)
o
if
2

f

exp(i kr) l

2
exp(i kr)=1+i kr+
1
2
(i kr)
2
+
probability of transition
exp(i kr)1
dipole transition; higher orders: electric quadrupole, magnetic dipole, etc ...
in the dipole approximation:
-- dipole operator
hence
For degenerate states:
where the sum is over all substates of the lower and upper levels
w
if
=
1
2
B
if
J (o
if
)=
4n
2
3c
2
d
if
2
J (o
if
) d
if
2
=(d
x
)
if

2
+(d
y
)
if

2
+(d
z
)
if

2
de

j
r
j
B
ul
=
8n
2
d
ul

2
3c
2
A
ul
=
64n
4
+
3
3hc
3
d
ul

2
A
ul
=
64n
4
+
ul
3
3 hc
3
1
g
u

d
ul

2
(d
x
)
if

2
= f e xi
2
Oscillator strength
Absorption
B
lu
=
4n
2
e
2
h +
ul
mc
f
lu
f
lu
=
2m
3
2
g
l
e
2
( E
u
E
l
)

d
lu

2
classically:
c
tot
=
ne
2
mc
=B
lu
classic
h+
lu
4n
B
lu
classic
=
4n
2
e
2
h+
lu
mc
f oscillator strength quantum correction to the classical value of B
Emission
B
ul
=
4n
2
e
2
h+
lu
mc
f
ul
g
l
f
lu
=g
u
f
ul
g
u
A
ul
=
8n
2
e
2
+
ul
2
mc
3
g
u
f
ul
=
8n
2
e
2
+
ul
2
mc
3
g
l
f
lu
Oscillator strength for emission are
negative
Natural line width
Energy levels are somewhat broadened as a result of of Heisenberg's
uncertainty principle. Finite life-time of a level means some spread in energy,
Level lifetime,
transition,
hence profile in frequency space (Fourier transform)
Long-lived levels give very narrow lines (e.g. H 21 cm line)
AE At
At 1/ A
21
1/
E(t )sin(2n+
0
t +
0
)e
t/2
(+)=
/ 4n
2
(++
0
)
2
+(/ 4n)
2
Radiative transitions
Permitted (allowed) transitions: dipole matrix element does not vanish
Semi-forbidden transitions: dipole transitions but with a change of spin
Forbidden transitions: dipole matrix element vanishes (may be possible at higher orders)
Selection rules
exp(i kr)=1+i kr+
Transitions with spin flip
Intercombination (semi-forbidden) lines

3
S
3
P
3
P
o

3
D
1
S
1
P
1
P
o

1
D
Grotrian diagram
CIII] 1909 , 6.50 eV (2s2p2s
2
)
The He-like ions line triplet

3
S
3
P
o

3
D
1
S
1
P
o

1
D
Ground state: 1s
2

1
S
0
1s2p
1
P
1
permitted (resonance) line (L=1, S=0, J=1)
1s2p
3
P
1
intercombination (L=1, S=1, J=1)
1s2s
3
S
1
forbidden (magnetic dipole) (L=0, S=1, J=1)
1s2p
3
P
2
magnetic quadrupole (L=1, S=1, J=2)
Forbidden lines
Example: [OIII] 5007 line

3
S
3
P
3
P
o

3
D
3
D
o

1
S
1
P
1
P
o 1
D
1
D
o
configuration: 2s
2
2p
2
2s
2
2p
2
line components:
4931
3
P
0

1
D
2
, E2
4959
3
P
1

1
D
2
, M1, E2
5007 ,
3
P
2

1
D
2
, M1, E2
AL=1, AS=1, AJ =2
AL=1, AS=1, AJ =1
AL=1, AS=1, AJ =0
Strictly forbidden transitions
Matrix element vanishes to all perturbational orders.
Example: Ly radiative decay of hydrogen: 2s to 1s two spherically symmetric wave
functions.
Possibilities:
collisional shifting 2s2p, then 2p1s. A = 6.210
8
s
-1
two-photon process: A = 8.2 s
-1
2-photon dominates if n<10
4
cm
-3
.
+++' =+
21
Transition rates: bound bound, hydrogen
A simple case: Hydrogen
h+=Ry(n
2
n'
2
) Ry
e
2
(2a
0
)
=13.6eV
Bound-bound transitions
Lyman- transition:
other Lyman series:
Absorption:
Absorption cross section (at the line center, assuming the natural line width only):
g f =
2
14
3
9
=0.83 A
21
=510
8
s
1
g
1
f
1n
=
2
9
n
5
(n1)
2n4
3( n+1)
2n+4
; n1 g
1
f
1n

1
n
3
B
12
=8.3 A
21
=4.210
9
s
1
c
+
=B
12
h +
4n
(+)10
11
cm
2
Transition rates: bound bound
Number of absorptions:
n
i
R
ij
=n
i
B
ij

+
J
+
d +n
i
B
ij

J
ij
=n
i
4no
ij

J
ij
h +
=n
i
4n

o
ij
(+)
J
+
h+
d +
Number of stimulated emissions:
n
j
B
ji

+
J
+
d +=n
j
B
ji

J
ij
=n
j
g
i
g
j
B
ij

J
ij
=n
j
4n
g
i
g
j
o
ij

J
ij
h+
Number of spontaneous emissions:
n
j
A
ji

+
d +=n
j
2h+
ij
3
c
2
B
ji
=n
j
2h+
ij
3
c
2
4n
g
i
g
j
o
ij
4n
o
ij
c
+
Transition rates: bound free
Bound-free transitions (photoionization)
E
f
=oX
Final energy of the electron:
Cross section:
more accurate form: Gaunt factor 1

for 1
2
S level of H-like ions (Osterbrock 1989):
Number of photoionizations:
c
bf

(2o)
9/ 2
nZ
5
c
7/2
3a
0
3/ 2
o
7/ 2
oX
c
bf
=
512n
7
me
10
Z
4
3
.
3 ch
6
n
5
g (o, n , l , Z)
o
3
c
bf
=
A
0
Z
2 (
+
1
+
)
4
exp
(
4
4arctanc
c
)
1exp(2n/ c)
, ++
1
A
0
=
2
8
n
3 e
4
(
1
137.0
)
na
0
2
=6.3010
18
cm
2
c=
.
+
+
1
1
h +
1
=Z
2
h+
0
=13.6 Z
2
eV
n
i
R
ik
=n
i
4n

+
0

o
ik
(+)
J
+
h+
d +
Transition rates
Radiative recombination the inverse process to photoionization
Number of recombinations (spontaneous + stimulated), obtained from the principle of detailed balance:
Collisional rates: excitation/deexcitation, ionization/three body recombination
n
k
(
R'
ki , spon
+R'
ki , stim
)
n
k
(
n
i
n
k
)
R
ki
=n
k
(
n
i
n
k
)
4n

+
0

o
ik
(+)
h+
(
2 h+
3
c
2
+

J
)
e
h+/ kT
d +
k ion
i atom

+
J
+
d +
sometimes used: recombination coefficient:
n
k
(
R'
ki , spon
+R'
ki , stim
)
n
k
n
e
o
RR
(T )
n
i
C
ij
=n
i
n
e

v
0

c
ij
(v) f (v) vdvn
i
n
e
q
ij
(T )
1
2
m
e
v
0
2
=E
0
- threshold for the ionization
Downward rates:
in equilibrium: hence:
n
i
C
ij
=n
j
C
ji
n
j
C
ji
=n
j
(n
i
/ n
j
)C
ij
=n
j
(n
i
/ n
j
) n
e
q
ij
(T )
Upward rate i->j, where j is a bound or free state:
Collisional transitions
Autoionization
Dielectronic recombination
Doubly excited states - two electrons in
excited levels may have energy
higher than the ionization potential of
the ion in ground state. Then
autoionization energetically
favorable. One electron leaves the ion,
the other returns to the ground state.
An ion collides with with an energetic electron:
doubly excited state may form. This may
autoionize, or a radiative downward transition
can take place, leaving a bound atom with a
single excited electron.
He
0
(1s
2
) + e He
-
(1s 2p
2
)
He
-
(1s 2p
2
) He
0
(1s
2
2p) + h
1
(satellite line)
He
-
(1s
2
2p) He
0
(1s
2
2s) + h
2
Fluorescence/Auger effect
An electron is removed from an inner (e.g., K) shell
and a highly excited ion is formed. This may decay
with the emission of a fluorescent line (e.g. K
line). Or, the excitation energy may be used to
eject a number of electrons (Auger process).