1990 Bruce Gold Medal

1937 AJC Prize

Spectroscopy
Spectral lines
The Fraunhofer spectrum
Charlotte Moore Sitterly
Multiplet table
Rowland table

Formalism of spectroscopy

Quantum Numbers of Atomic States

Principal quantum number n defines the energy level

Azimuthal quantum number l

orbits of s states become more eccentric as n increases

Electron transitions take place between adjacent angular
momentum states (i.e. l=1)

l=0 called s states

l=1 called p states
l=2 called d states
l=3 called f states

states with
states with
states with
states with

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

For s states, j=1/2
For p states, j=1/2 or j=3/2

Electron levels are designated by the notation n 2(L)J

For the sodium ground level is 3s2S1/2

The two lowest p levels are 3p2P1/2 and 3p2P

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

3/2

The Na D lines are described

3s2S - 3p2P3/2 5889.953 and 3s2S - 3p2P1/2 5895.923
* 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, 1s22s22p2says 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 l=1 and J=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

NIST

Grotrian
Diagram for
OI

Fraunhofer Lines
Lines

Due To ...

Wavelengths ()

A - (band)

O2 (telluric)

7594 - 7621

B - (band)

O2 (telluric)

6867 - 6884

H-alpha

6563

a - (band)

O2 (telluric)

6276 - 6287

D - 1, 2

Na

5896 & 5890

Fe

5270

b - 1, 2

Mg

5184 & 5173

Fe

4958

H-beta

4861

Fe

4668

Fe

4384

H-gamma

4340

G (band)

Fe & Ca , CH

4308

Ca

4227

H-delta

4102

Ca

3968

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 arent 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 0 2
4

mc ( 0 ) 2 ( 4 ) 2
N0 is the number of bound electrons per unit volume
the quantity -0 is the frequency separation from the
nominal line center
the quantity is the dielectric constant (=1 in free space)
and g/m is the classical damping constant

The atomic absorption coefficient includes atomic

data (f, , ) 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 0 2
4

mc ( 0 ) 2 ( 4 ) 2
For a classical harmonic oscillator,
The shape of the spectral line depends on the size of the classical
damping constant
For -0 >> /4, the line falls off as (-0)-2
Accelerating electric charges radiate.

dW
8 2 2 2

W
3
dt
3mc
and

W W0 e

8 2 2 2 0.2223 1

sec
3
2
3mc

is the classical damping constant ( is in cm)

The mean lifetime is

also defined as T=1/,
where T=4.5 2

2
N

4
The Classical Damping 0
2
2
mc
(

)
0
Line Profile

The Classical Line Profile

Look at a thin atmospheric layer between 2 (the deeper
layer) and 1

I ( 2 ) I ( 1 )e x I ( 1 )(1 x)
I ( 2 ) I ( 1 ) xI ( 1 )

The line profile is proportional

to

At line center =0, and

Half the maximum depth occurs at (-0)=/4
In terms of wavelength
2
4

mcN

c
c
2 2
2 1 2

0.000118 A
2
2

4 3mc

Very small and the same for ALL lines!

An example

N 0 2
4

mc ( 0 ) 2 ( 4 ) 2
8 2 2 2 0.2223 1

sec
3
2
3mc

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

= 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:
0- = 1.7 x 1011 sec-1 and
N = 1/ = 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 quantityx is a column density

Natural Broadening
From Heisenberg's uncertainty principle: The electron in an excited
state is only there for a short time, so its energy cannot have a precise
value.
Since energy levels are "fuzzy," atoms can absorb photons with slightly
different energy, with the probability of absorption declining as the
difference in the photon's energy from the "true" energy of the
transition increases.
The FWHM of natural broadening for a transition with an average
waiting time of to is given by

2 1
(1 / 2 )
c to

A typical value of ()1/2 = 2 x 10-4 A. Natural broadening is usually very

small.
The profile of a naturally broadened linen is given by a dispersion
profile (also called a damping profile, a Lorentzian profile, a Cauchy
curve, and the Witch of Agnesi!) of the form (in terms of frequency)

where is the "damping constant."

I
( 0 ) 2 2

The Classical Damping Constant

N 0 2
4

mc ( 0 ) 2 ( 4 ) 2
For a classical harmonic oscillator,
The shape of the spectral line depends on the size of the classical
damping constant
For -0 >> /4, the line falls off as (-0)-2
Accelerating electric charges radiate.

dW
8 2 2 2

W
3
dt
3mc
and

W W0 e

8 2 2 2 0.2223 1

sec
3
2
3mc

is the classical damping constant ( is in cm)

The mean lifetime is

also defined as T=1/,
where T=4.5 2

Line Absorption with QM

Replace with !
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

Add Quantum Mechanics

Define the oscillator strength, f:
related to the atomic transition

probability Bul:

e 2
d
f
mc

d hBlu

mc
mc 3 g u
7 Blu
15 2 g u
f 2 hBul 7.5 x10

Aul 1.9 x10

Aul
2 2
e
2e g l
gl

f-values usually tabulated as gf-values.

theoretically calculated
laboratory measurements
solar

Collisional Broadening
Perturbations by discrete encounters
Change in energy approximated by a power law of the form

E = constant x r-n

(r is the separation between the atom and the perturber)

Perturbations by static ion fields (linear Stark effect
broadening) (n=2)
Self-broadening - collisions with neutral atoms of the same kind
(resonance broadening, n=3)
if perturbed atom or ion has an inner core of electrons (i.e. with
a dipole moment) (quadratic Stark effect, n=4)
Collisions with atoms of another kind (neutral hydrogen atoms)
(van der Waals, n=6)
Assume adiabatic encounters (electron doesnt change level)
Non-adiabatic (electron changes level) collisions also possible

Pressure Broadening E=constant x r-n

n

Type

Lines Affected Perturber

Linear Stark

Hydrogen

Protons, e-

Common
species

Atoms of the
same type

Self broadening or
resonance
broadening
Quadratic Stark

Most, esp. in
hot stars

Ions, e-

Van der Waals

Most, esp. in
cool stars

Neutral
hydrogen

Approaches to Collisional Broadening

Statistical effects of many particles (pressure broadening)
Usually applies to the wings, less important in the core
Some lines can be described fully by one or the other
Know your lines!
The functional form for collisional damping is the same as for
radiation damping, but rad is replaced with coll

e 2
4 2

f
mc ( 2 ( 4 ) 2
Collisional broadening is also described with a dispersion function
Collisional damping is sometimes 10s of times larger than
radiation damping

Damping Coefs for Na D

2
7
log 6 19.6 log C6 ( H ) log Pg log T
5
10
2
5
log 4 19.4 log C4 log Pe log T
3
6

Doppler Broadening

Two components contribute to the intrinsic Doppler broadening of

spectral lines:
Thermal broadening
Turbulence the dreaded microturbulence!
Thermal broadening is controlled by the thermal velocity distribution
(and the shape of the line profile)
2

dN (vr ) m

N Total
2kT

mvr 2

2 kT

dvr

where vr is the line of sight velocity component

The Doppler width associated with the velocity v 0 (where the variance
v02=2kT/m) is

v0
2kT
D

c
c m

and is the wavelength of line center

4.3 x10 (T )
7

More Doppler Broadening

Combining these we get the thermal broadening line profile:

I
I total

m
e
2kT

2 2 kT

At line center, =0, and this reduces to

I
I total

mc 2 ( 0 ) 2

m
2kT

Where the line reaches half its maximum depth, the total width is

21 2

20

2kT ln 2
m

Thermal + Turbulence
The average speed of an atom in a gas due to thermal motion Maxwell Boltzmann distribution. The most probably speed is
given by

vmp 2kt / m

Moving atoms are Doppler shifted, and individual atoms will

absorb light at slightly different wavelengths because of the
Doppler shift.
Spectral lines are also Doppler broadened by turbulent motions
in the gas. The combination of these two effects produces a
Doppler-broadened profile:

( )1/ 2

2 2kT
2

vturb ln 2

c m

Typical values for 1/2 are a few tenths of an Angstrom. The

line depth for Doppler broadening decreases exponentially from
the line center.

Combining the Natural, Collisional and Thermal

Broadening Coefficients

The combined broadening coefficient is just the convolution of all of the

individual broadening coefficients
The natural, Stark, and van der Waals broadening coefficients all have the
form of a dispersion profile:

b
a
2 b 2

With damping constants (rad, 2, 4, 6) one simply adds them up to get the
total damping constant:

total 4 2
e 2

f
mc 2 ( total 4 ) 2

The thermal profile is a Gaussian profile:

1
1 2
e
D

The Voigt Profile

The convolution of a dispersion profile and a Gaussian profile
is known as a Voigt profile.

V ( , D , )

4 2
1
e
2
2
12
( 1 ) ( 4 ) D

d 1

Voigt functions are tabulated for use in computation

In general, the shapes of spectra lines are defined in terms of
Voigt profiles
Voigt functions are dominated by Doppler broadening at small
, and by radiation or collisional broadening at large
For weak lines, its the Doppler core that dominates.
In solar-type stars, collisions dominate , so one needs to know
the damping constant and the pressure to compute the line
absorption coefficient
For strong lines, we need to know the damping parameters to
interpret the line.

Calculating Voigt Profiles

V (u, a)

1
v D

2 / c
H (u, a)
H (u , a)

Tabulated as the Hjerting function H(u,a)

u=/D
a=(2/4c)/D =(/4)D

Hjertung functions are expanded as:

H(u,a)=H0(u) + aH1(u) + a2H2(u) + a3H3(u) +
or, the absorption coefficient
2 is
2

e f

H (u , a )
2
mc
D

Plot a Damped Profile

1.2
1

Line Strength

0.8
0.6
0.4
Line Profiles

0.2

Natural + Thermal
Natural + Thermal + Collisional

0
-5

-4

-3

-2

-1

Doppler Widths