1990 Bruce Gold Medal

1937 AJC Prize

Spectroscopy
• Spectral lines
• The Fraunhofer spectrum
• Charlotte Moore Sitterly (Allen!)
– Multiplet table
– Rowland table
• Formalism of spectroscopy
Quantum Numbers of Atomic States
• Principal quantum number n defines the energy level
• Azimuthal quantum number l
– states with l=0 called s states
– states with l=1 called p states
– states with l=2 called d states
– states with l=3 called f states
• “orbits” of s states become more eccentric as n increases
• Electron transitions take place between adjacent angular
momentum states (i.e. Dl=1)
– “sharp series” lines from p to higher s states
– “principal series” lines from s to higher p states
– “diffuse series” lines from p to higher d states
– “fundamental series” lines from d to higher f states
• The first line(s) of the principal series (s to p) are called resonance
lines since it involves the ground level
• In alkali metals, the p, d, and f energy levels are doubled (e.g. the
Na D lines) due to the coupling between the magnetic moment of
the orbital motion and the spin of the electron (the quantum
number s, which can be +1/2 or –1/2
 Spectroscopic Notation
• The total angular momentum quantum number is j = l +S*
– For s states, j=1/2
– For p states, j=1/2 or j=3/2

• Electron levels are designated by the notation “n2(L)J”

• n is the total quantum number
• The superscript 2 indicates the levels are doubled
• L is the azimuthal quantum number (S,P,D,F)
• J denotes the angular momentum quantum number

• For the sodium ground level is 3s2S1/2

• The two lowest p levels are 3p2P1/2 and 3p2P 3/2
• The Na D lines are described
• 3s2S½ - 3p2P3/2 l5889.953 and 3s2S½ - 3p2P1/2 l5895.923

* This is a different S than the s state!

 More Spectroscopic Vocabulary

• The Pauli exclusion principle requires that two s-electrons in

the same state must have opposite spin
• Therefore S=0 and these are called “singlet” states
• The ground state of He is a singlet state – 1S0
– The superscript 1 means singlet
– The subscript 0 means J=0
• In the first excited state of He, one electron is in the 1s
state, and the second can be in either the 2s or the 2p
state.
• Depending on how the electrons’ spins are aligned, these
states can either be singlets or triplets
• Electrons can only jump between singlet states or between
triplet states
 It goes on and on and on…
• The state of the electrons is described with a term for each
electron above the closed shell.
• For carbon atoms, “1s22s22p2”says there are
– 2 electrons in the 1s state
– 2 electrons in the 2s state
– 2 electrons in the 2p state
• Allowed and forbidden transitions
– Transitions with Dl=1 and DJ=1 and 0 are allowed (except
between J=0 and J=0)
– Other transitions are forbidden
– For some electron states there are no allowed transitions to
lower energy states. Such levels are called metastable
– The situation is more complex in atoms with more electrons
– A multiplet is the whole group of transitions between two
states, say 3P-3D
 Grotrian
Diagram for
He

• Struve and Wurm

1938, ApJ
 Grotrian
Diagram for
Li I

NIST
 Grotrian
Diagram for
NIST OI
 Fraunhofer Lines
Lines Due To ... Wavelengths (Å)
A - (band) O2 (telluric) 7594 - 7621
B - (band) O2 (telluric) 6867 - 6884
C H-alpha 6563
a - (band) O2 (telluric) 6276 - 6287
D - 1, 2 Na 5896 & 5890
E Fe 5270
b - 1, 2 Mg 5184 & 5173
c Fe 4958
F H-beta 4861
d Fe 4668
e Fe 4384
f H-gamma 4340
G (band) Fe & Ca , CH 4308
g Ca 4227
h H-delta 4102
H Ca 3968
K Ca 3934
 Spectral Line Formation

• Classical picture of radiation

• Intrinsic vs. extrinsic broadening
mechanisms
• Line absorption coefficient
• Radiative transfer in spectral lines
 Spectral Line Formation-Line
Absorption Coefficient
• Radiation damping (atomic absorptions and
emissions aren’t perfectly monochromatic –
uncertainty principle)
• Thermal broadening from random kinetic
motion
• Collisional broadening – perturbations from
neighboring atoms/ions/electrons)
• Hyperfine structure
• Zeeman effect
 Classical Picture of Radiation

• Photons are sinusoidal variations of

electro-magnetic fields
• When a photon passes by an electron
in an atom, the changing fields cause
the electron to oscillate
• Treat the electron as a classical
harmonic oscillator:
mass x acceleration =
external force – restoring force – dissipative

• E&M is useful! (well…)

 Atomic Absorption Coefficient

N 0e 2 g 4
n  =
mc (n n 0 ) 2  (g 4 ) 2
• N0 is the number of bound electrons per unit volume
• the quantity n-n0 is the frequency separation from the
nominal line center
• the quantity e is the dielectric constant (e=1 in free space)
• and g=g/m is the classical damping constant

The atomic absorption coefficient includes atomic

data (f, e, g) and the state of the gas (N0), and is a
function of frequency. The equation expresses the
natural broadening of a spectral line.
 The Classical Damping Constant
N 0e 2 g 4
n  =
mc (n n 0 ) 2  (g 4 ) 2

• For a classical harmonic oscillator,

• The shape of the spectral line depends on the size of the
classical damping constant
• For n-n0 >> g/4, the line falls off as (n-n0)-2
• Accelerating electric charges radiate.

dW 8 2n 2e 2 W = W0 e gt
= 3
W
dt 3mc
The mean lifetime is
• and 8 2n 2e 2 0.2223 1 also defined as T=1/g,
g= = sec where T=4.5l2
3mc 3
l2

• is the classical damping constant (l is in cm)

The Classical Damping n  = 0
N e 2
g 4
Line Profile mc (n  n 0 ) 2
 (g 4 ) 2
 The Classical Line Profile
• Look at a thin atmospheric layer between t2 (the
deeper layer) and t1

In (t 2 ) = In (t 1 )e n Dx  In (t 1 )(1  n Dx)

In (t 2 )  In (t 1 )  n DxIn (t 1 )
• The line profile is proportional to n
• At line center n=n0, and n  = mcg
4e 2 N

• Half the maximum depth occurs at (n-n0)=g/4

• In terms of wavelength

c c g 2e 2
Dl 1 = Dn 1 = 2 = = 0.000118 A
2 n 2
2 n 4 3mc 2

• Very small – and the same for ALL lines!

 N 0e 2 g 4
An example… n  =
mc (n n 0 ) 2  (g 4 ) 2
8 2n 2e 2 0.2223 1
g= = sec
3mc 3
l2

• The Na D lines have a wavelength of 5.9x10-5 cm.

g = 6.4 x 107 sec-1

• The absorption coefficient per gram of Na atoms at a

distance of 2A from line center can be calculated:
Dn0-n = 1.7 x 1011 sec-1 and
N = 1/m = 2.6 x 1022 atoms gm-1

• Then  = 3.7 x 104 f

• and f=2/3, so

 = 2.5 x 104 per gram of neutral sodium

 The Abundance of Sodium

• In the Sun, the Na D lines are about 1% deep

at a distance of 2A from line center
• Use a simple one-layer model of depth x (the
Schuster-Schwarzschild model)
I
= e x = 0.99
I0
• Or x=0.01, and x=4x10-7 gm cm-2 (recall
that Na=2.5 x 104 per gram of neutral sodium
at a distance of 2A from line center)
• the quantity x is a column density
 Line Absorption with QM
• Replace g with G!
• Broadening depends on lifetime of level
• Levels with long lifetimes are sharp
• Levels with short lifetimes are fuzzy
• QM damping constants for resonance lines
may be close to the classical damping
constant
• QM damping constants for other
Fraunhofer lines may be 5,10, or even 50
times bigger than the classical damping
constant