Atomic Spectroscopy

W. C. Martin and W. L. Wiese

National Institute of Standards and Technology

Gaithersburg, Maryland 20899

Originally published as Chapter 10 in Atomic, Molecular, and Optical Physics Handbook, G.W.F. Drake, Ed. (AIP

Press, Woodbury, NY, 1996). Minor style changes have been made in this web version.

Note: Links are not underlined on this page to improve readability.

1. Introduction

2. Frequency, Wavenumber, Wavelength

3. Atomic States, Shells, and Configurations

4. Hydrogen and Hydrogen-like Ions

5. Alkalis and Alkali-like Spectra

6. Helium and Helium-like Ions; LS Coupling

7. Hierarchy of Atomic Structure in LS Coupling

8. Allowed Terms of Levels for Equivalent Electrons

LS Coupling

jj Coupling

9. Notations for Different Coupling Schemes

LS Coupling (Russell-Saunders Coupling)

jj Coupling of Equivalent Electrons

J

1

 j or J

1

 J2 Coupling

J

1

 l or J

1

 L2 Coupling (J

1

 K Coupling)

LS1 Coupling (LK Coupling)

Coupling Schemes and Term Symbols

10. Eigenvector Composition of Levels

11. Ground Levels and Ionization Energies for the Neutral Atoms

12. Zeeman Effect

13. Term Series, Quantum Defects, and Spectral-line Series

14. Sequences

Isoelectronic Sequence

Isoionic, Isonuclear, and Homologous Sequences

15. Spectral Wavelength Ranges, Dispersion of Air

16. Wavelength (Frequency) Standards

17. Spectral Lines: Selection Rules, Intensities, Transition Probabilities, Values, and Line Strengths

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Emission Intensities (Transition Probabilities)

Absorption f values

Line Strengths

Relationships between A, f, and S

Relationships between Line and Multiplet Values

Relative Strengths for Lines of Multiplets in LS Coupling

18. Atomic Lifetimes

19. Regularities and Scaling

Transitions in Hydrogenic (One-Electron) Species

Systematic Trends and Regularities in Atoms and Ions with Two or More Electrons

20. Spectral Line Shapes, Widths, and Shifts

Doppler Broadening

Pressure Broadening

21. Spectral Continuum Radiation

Hydrogenic Species

Many-Electron Systems

22. Sources of Spectroscopic Data

23. References

 

1. INTRODUCTION

This article outlines the main concepts of atomic structure, with some emphasis on terminology and

notation. Atomic radiation is discussed, in particular the wavelengths, intensities, and shapes of spectral

lines, and a few remarks are made regarding continuous spectra. We include updated tabulations of

ionization energies for the neutral atoms and transition probabilities for persistent lines of selected neutral

atoms. Some sources of additional atomic spectroscopic data are mentioned. 

Experimental techniques and the details of atomic theoretical methods are not covered in this article;

these and a number of other subjects pertinent to atomic spectroscopy are treated in one or more of at

least fifteen chapters in the volume Atomic, Molecular, and Optical Physics Handbook, G.W.F. Drake,

Ed. (AIP Press, Woodbury, NY, 1996) and in references below. 

 

2. FREQUENCY, WAVENUMBER, WAVELENGTH

The photon energy due to an electron transition between an upper atomic level k (of energy Ek) and a

lower level i is 

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Atomic Spectroscopy: An Introduction
E = Ek

 - Ei = h = hc = hc/

vac , (1) 

where is the frequency, the wavenumber in vacuum, and vac the wavelength in vacuum. The most

accurate spectroscopic measurements are determinations of transition frequencies, the unit being the

Hertz (1 Hz = cycle/sec) or one of its multiples. A measurement of any one of the entities frequency,

wavenumber, or wavelength (in vacuum) is an equally accurate determination of the others since the

speed of light is exactly defined. The most common wavelength units are the nanometer (nm), the

Ångström (1 = 10-1 nm) and the micrometer (μm). The SI wavenumber unit is the inverse meter, but in

practice wavenumbers are usually expressed in inverse centimeters: 1 cm-1 = 102 m-1, equivalent to

2.997 924 58 x104 MHz. 

In addition to frequency and wavenumber units, atomic energies are often expressed in electron volts

(eV). One eV is the energy associated with each of the following quantities: 

2.417 988 4(7) x1014 Hz

8 065.541 0(24) cm-1

1 239.842 44(37) nm

11 604.45(10) K (kelvin)

1.602 177 3(5) x10-19 J (joule) 

We note that the basic unit of temperature, the kelvin, is equivalent to about 0.7 cm-1, i.e., the value of

the Boltzmann constant k expressed in wavenumber units per kelvin is 0.695 039(6) cm-1/K. One reason

for citing this particular equivalency involving the internationally accepted symbol for the kelvin (K) [1] is

to suggest that use of the letter K as a symbol for 1 cm-1 (1 kayser) should be discontinued. 

The unit of energy in the system of atomic units (a.u.) often used for theoretical calculations is the

hartree, which is equal to 2 rydbergs. The rydberg for an atom having nuclear mass M is 

1 Ry = RM = M(M + me)

-1 R , (2) 

with 

R = mec

2

/(2h) = 10 973 731.568 62(9) m-1 , (3) 

which is equivalent to 13.605 698(4) eV. The Rydberg constant R is thus the limit value for infinite

nuclear mass. 

 

3. ATOMIC STATES, SHELLS, AND CONFIGURATIONS

A one-electron atomic state is defined by the quantum numbers nlmlms or nljmj, with n and l representing

the principal quantum number and the orbital angular momentum quantum number, respectively. The

allowed values of n are the positive integers, and l = 0, 1, ..., n - 1. The quantum number j represents the

angular momentum obtained by coupling the orbital and spin angular momenta of an electron, i.e.,

j = l + s, so that j = l ± 1/

2

. The magnetic quantum numbers ml, ms, and mj represent the projections of

the corresponding angular momenta along a particular direction; thus, for example, ml = -l, -l + 1 ... l and

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Atomic Spectroscopy: An Introduction
ms

 = ± 1/

2

. 

The central field approximation for a many-electron atom leads to wave functions expressed in terms of

products of such one-electron states [2], [3]. Those electrons having the same principal quantum number

n belong to the shell for that number. Electrons having both the same n value and l value belong to a

subshell, all electrons in a particular subshell being equivalent. The notation for a configuration of N

equivalent electrons is nlN, the superscript usually being omitted for N = 1. A configuration of several

subshells is written as nlNn l

M ... . The numerical values of l are replaced by letters in writing a

configuration, according to the code s, p, d for l = 0, 1, 2 and f, g, h ... for l = 3, 4, 5 ..., the letter j being

omitted. 

The Pauli exclusion principle prohibits atomic states having two electrons with all four quantum numbers

the same. Thus the maximum number of equivalent electrons is 2(2l + 1). A subshell having this number

of electrons is full, complete, or closed, and a subshell having a smaller number of electrons is unfilled,

incomplete, or open. The 3p

6

 configuration thus represents a full subshell and 3s

2

 3p

6

 3d

10 represents a

full shell for n = 3. 

The parity of a configuration is even or odd according to whether il

i

 is even or odd, the sum being taken

over all electrons (in practice only those in open subshells need be considered).

4. HYDROGEN AND HYDROGEN-LIKE IONS

The quantum numbers n, l, and j are appropriate [4]. A particular level is denoted either by nlj or by

nl 2LJ with L = l and J = j. The latter notation is somewhat redundant for one-electron spectra, but is

useful for consistency with more complex structures. The L values are written with the same letter code

used for l values, but with roman capital letters. The multiplicity of the L term is equal to

2S + 1 = 2s + 1 = 2. Written as a superscript, this number expresses the doublet character of the

structure: each term for L 1 has two levels, with J = L ± 1/

2

, respectively. 

The Coulomb interaction between the nucleus and the single electron is dominant, so that the largest

energy separations are associated with levels having different n. The hyperfine splitting of the 1H 1s

ground level [1420.405 751 766 7(10) MHz] results from the interaction of the proton and electron

magnetic moments and gives rise to the famous 21 cm line. The separations of the 2n - 1 excited levels

having the same n are largely determined by relativistic contributions, including the spin-orbit interaction,

with the result that each of the n - 1 pairs of levels having the same j value is almost degenerate; the

separation of the two levels in each pair is mainly due to relatively small Lamb shifts. 

 

5. ALKALIS AND ALKALI-LIKE SPECTRA

In the central field approximation there exists no angular-momentum coupling between a closed subshell

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Atomic Spectroscopy: An Introduction
and an electron outside the subshell, since the net spin and orbital angular momenta of the subshell are

both zero. The nlj quantum numbers are, then, again appropriate for a single electron outside closed

subshells. However, the electrostatic interactions of this electron with the core electrons and with the

nucleus yield a strong l-dependence of the energy levels [5]. The differing extent of "core penetration" for

ns and np electrons can in some cases, for example, give an energy difference comparable to or exceeding

the difference between the np and (n + 1)p levels. The spin-orbit fine-structure separation between the nl

(l > 0) levels having j = l - 

1

/

2

 and l + 1/

2

, respectively, is relatively small. 

 

6. HELIUM AND HELIUM-LIKE IONS; LS COUPLING

The energy structure of the normal 1snl configurations is dominated by the electron-nucleus and

electron-electron Coulomb contributions [4]. In helium and in helium-like ions of the lighter elements, the

separations of levels having the same n and having l = s, p, or d are mainly determined by direct and

exchange electrostatic interactions between the electrons - the spin-orbit, spin-other orbit, and other

relativistic contributions are much smaller. This is the condition for LS coupling, in which: 

(a) The orbital angular momenta of the electrons are coupled to give a total orbital angular

momentum L = il

i

.

(b) The spins of the electrons are coupled to give a total spin S = is

i

. 

The combination of a particular S value with a particular L value comprises a spectroscopic term, the

notation for which is 2S+1L. The quantum number 2S + 1 is the multiplicity of the term. The S and L

vectors are coupled to obtain the total angular momentum, J = S + L, for a level of the term; the level is

denoted as 2S+1LJ. 

For 1snl configurations, L = l and S = 0 or 1, i.e., the terms are singlets (S = 0) or triplets (S = 1). As

examples of the He I structure, the ionization energy (energy required to remove one of the 1s electrons

in the 1s

2

 ground configuration) is 24.5874 eV, the 1s2s

3S - 1S separation is 0.7962 eV, the

1s2p 3P° - 1P° separation is 0.2539 eV, and the 1s2p

3P°2

 - 

3P°0

 fine-structure spread is only

1.32 x 10-4 eV. 

7. HIERARCHY OF ATOMIC STRUCTURE IN LS

COUPLING

The centrality of LS coupling in the analysis and theoretical interpretation of atomic spectra has led to the

acceptance of notations and nomenclature well adapted to discussions of particular structures and spectra

[2]. The main elements of the nomenclature are shown in the table below, most of the structural entities

having already been defined in the above discussions of simple spectra. The quantum numbers in the table

represent a full description for complex configurations, and the accepted names for transitions between

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Atomic Spectroscopy: An Introduction
the structural elements are also given. 

 

Atomic structural hierarchy in LS coupling and names for the groups of all

transitions between structural entities.

Structural

entity

Quantum

numbersa

Group of all

transitions

Configuration (n

i

l

i

)

Ni Transition array

Polyad (n

i

l

i

)

Ni S

1

 L1 nl S L, S L ... Supermultiplet

Term (n

i

l

i

)

Ni S L Multiplet

Level (n

i

l

i

)

Ni S L J Line

State (n

i

l

i

)

Ni S L J M Line component

aThe configuration may include several open subshells, as indicated by the i

subscripts. The letter represents any additional quantum numbers, such as

ancestral terms, necessary to specify a particular term.

As an example, the Ca I 3d4p

3D°2

level belongs to the 3D° term which, in turn, belongs to the

3d4p

3

(P° D° F°) triplet triad. The 3d4p configuration also has a 1(P° D° F°) singlet triad. The 3d4s

configuration has only monads, one 1D and one 3D. The 3d4s

3D2

 - 3d4p

3D°3

line belongs to the

corresponding 3D - 3D° triplet multiplet, and this multiplet belongs to the great Ca I 3d4s

3D -

3d4p

3

(P° D° F°) supermultiplet of three triplet multiplets discussed by Russell and Saunders in their

classic paper on the alkaline-earth spectra [6]. The 3d4s - 3d4p transition array includes both the singlet

and triplet supermultiplets, as well as any (LS-forbidden) intercombination or intersystem lines arising

from transitions between levels of the singlet system and those of the triplet system. The order of the two

terms in the transitions as written above, with the lower-energy term on the left, is standard in atomic

spectroscopy. Examples of notations for complex configurations are given in Notations for Different

Coupling Schemes. 

8. ALLOWED TERMS OR LEVELS FOR EQUIVALENT

ELECTRONS

LS Coupling

The allowed LS terms of a configuration consisting of two nonequivalent groups of electrons are

obtained by coupling the S and L vectors of the groups in all possible ways, and the procedure may

be extended to any number of such groups. Thus the allowed terms for any configuration can be

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Atomic Spectroscopy: An Introduction
obtained from a table of the allowed terms for groups of equivalent electrons. 

The configuration l

N has more than one allowed term of certain LS types if l > 1 and 2 < N < 4l

(d

3

 - d

7

, f

3

 - f

11, etc.). The recurring terms of a particular LS term type from dN and fN

configurations are assigned sequential index numbers in the tables of Nielson and Koster [7]; the

index numbers stand for additional numbers having group-theoretical significance that serve to

differentiate the recurring terms, except for a few terms of f

5

 and f

9

, f

6

 and f

8

, and f

7

. These

remaining terms, which occur only in pairs, are further labeled A or B to indicate Racah's separation

of the two terms. 

The index numbers of Nielson and Koster are in practice the most frequently used labels for the

recurring terms of f

N configurations. Use of their index numbers for the recurring terms of dN

configurations has perhaps the disadvantage of substituting an arbitrary number for a quantum

number (the seniority) that itself distinguishes the recurring terms in all cases. The actual value of the

seniority number is rarely needed, however, and a consistent notation for the d

N and fN

configurations is desirable. A table of the allowed LS terms of the l

N electrons for l 3 is given in

Ref. [8], with all recurring terms having the index numbers of Nielson and Koster as a following

on-line integer. The theoretical group labels are also listed. Thus the d

3 2D term having seniority 3 is

designated 2D2, instead of D, in this scheme; and the level having J = 3/

2

 is designated 2D3/22.

jj Coupling

The allowed J values for a group of N equivalent electrons having the same j value, l

j

N, are given in

the table below for j = 1/

2

, 

3

/

2

, 

5

/

2

, and 7/

2

 (sufficient for l 3). The l

4

7/2 group has two allowed

levels for each of the J values 2 and 4. The subscripts distinguishing the two levels in each case are

the seniority numbers [9]. 

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Atomic Spectroscopy: An Introduction
Allowed J values for l

j

N equivalent electrons (jj

coupling).

l

j

N Allowed J values 

l

1/2

1

/

2

l

2

1/2 0

l

3/2 and l

3

3/2

3

/

2

l

2

3/2 0, 2

l

4

3/2 0

l

5/2 and l

5

5/2

5

/

2

l

2

5/2 and l

4

5/2 0, 2, 4

l

3

5/2

3

/

2

, 

5

/

2

, 

9

/

2

l

6

5/2 0

l

7/2 and l

7

7/2

7

/

2

l

2

7/2 and l

6

7/2 0, 2, 4, 6

l

3

7/2 and l

5

7/2

3

/

2

, 

5

/

2

, 

7

/

2

, 

9

/

2

, 

11/

2

, 

15/

2

l

4

7/2 0, 2

2, 42, 24, 44, 5, 6, 8 

l

8

7/2 0

The allowed levels of the configuration nl N may be obtained by dividing the electrons into sets of

two groups , Q + R = N. The possible sets run from Q = N - 2l (or zero if N < 2l) up to

Q = N or Q = 2l + 2, whichever is smaller. The (degenerate) levels for a set with both Q and R

nonzero have wave functions defined by the quantum numbers ( J

1

, J

2

) J, with J

1

 and J

2

 deriving

from the Q and R groups, respectively. The symbols and represent any additional quantum

numbers required to identify levels. The J values of the allowed levels for each ( J

1

, J

2

) subset are

obtained by combining J

1

 and J

2

 in the usual way. 

 

9. NOTATIONS FOR DIFFERENT COUPLING SCHEMES

The following examples make clear the meaning of the different coupling-scheme notations. Not all the

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Atomic Spectroscopy: An Introduction
configurations in the examples have been identified experimentally, and some of the examples of a

particular coupling scheme given for heuristic purposes may be physically inappropriate. Cowan [3]

describes the physical conditions for the different coupling schemes and gives experimental examples. 

LS Coupling (Russell-Saunders Coupling)

Some of the examples given below indicate notations bearing on the order of coupling of the

electrons. 

1. 3d

7 4F7/2

2. 3d

7

(

4F)4s4p(3P°) 6F°9/2

3. 4f

7

(

8S°)6s6p2

(

4P) 11P°5

4. 3p

5

(

2P°)3d2

(

1G) 2F°7/2

5. 4f

10(3K2)6s6p(1P°) 3L°6

6. 4f

7

(

8S°)5d (7D°)6p 8F°13/2

7. 4f

7

(

8S°)5d (9D°)6s (8D°)7s 9D°5

8. 4f

7

(

8S°)5d (9D°)6s6p(3P°) 11F8

9. 4f

7

(

8S°)5d2

(

1G) (8G°)6p 7F0

10. 4f(

2F°) 5d2

(

1G)6s (2G) 1P°1

In the second example, the seven 3d electrons couple to give a 4F term, and the 4s and 4p electrons

couple to form the 3P° term; the final 6F° term is one of nine possible terms obtained by coupling the

4F grandparent and 3P° parent terms. The next three examples are similar to the second. The

meaning of the index number 2 following the 3K symbol in the fifth example is explained in the

section LS Coupling. 

The coupling in example 6 is appropriate if the interaction of the 5d and 4f electrons is sufficiently

stronger than the 5d-6p interaction. The 7D° parent term results from coupling the 5d electron to the

8S° grandparent, and the 6p electron is then coupled to the 7D° parent to form the final 8F term. A

space is inserted between the 5d electron and the 7D° parent to emphasize that the latter is formed

by coupling a term (8S°) listed to the left of the space. Example 7 illustrates a similar coupling order

carried to a further stage; the 8D° parent term results from the coupling of the 6s electron to the 9D°

grandparent. 

Example 8 is similar to examples 2 through 5, but in 8 the first of the two terms that couple to form

the final 11F term, i.e., the 9D° term, is itself formed by the coupling of the 5d electron to the 8S°

core term. Example 9 shows an 8G° parent term formed by coupling the 8S° and 1G grandparent

terms. A space is again used to emphasize that the following (8G°) term is formed by the coupling of

terms listed before the space. 

A different order of coupling is indicated in the final example, the 5d

2

 

1G term being coupled first

to the external 6s electron instead of directly to the 4f core electron. The 4f (

2F°) core term is

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Atomic Spectroscopy: An Introduction
isolated by a space to denote that it is coupled (to the 5d

2

(

1G)6s 2G term) only after the other

electrons have been coupled. The notation in this particular case (with a single 4f electron) could be

simplified by writing the 4f electron after the 2G term to which it is coupled. It appears more

important, however, to retain the convention of giving the core portion of the configuration first. 

The notations in examples 1 through 5 are in the form recommended by Russell, Shenstone, and

Turner [10], and used in both the Atomic Energy States [11] and Atomic Energy Levels [8], [12]

compilations. The spacings used in the remaining examples allow different orders of coupling of the

electrons to be indicated without the use of additional parentheses, brackets, etc. 

Some authors assign a short name to each (final) term, so that the configuration can be omitted in

tables of classified lines, etc. The most common scheme distinguishes the low terms of a particular

SL type by the prefixes a, b, c, ..., and the high terms by z, y, x, ... [12]. 

jj Coupling of Equivalent Electrons

This scheme is used, for example, in relativistic calculations. The lower-case j indicates the angular

momentum of one electron (j = l ± 1/

2

) or of each electron in an l

j

N group. Various ways of

indicating which of the two possible j values applies to such a group without writing the j-value

subscript have been used by different authors; we give the j values explicitly in the examples below.

We use the symbols J

i

 and j to represent total angular momenta. 

1. (6p

2

1/2)0

2. (6p

2

1/2 6p3/2)°3/2

3. (6p

2

1/2 6p

2

3/2)2

4. 4d

3

5/2 4d

2

3/2 (9

/

2

, 2)11/2

The relatively large spin-orbit interaction of the 6p electrons produces jj-coupling structures for the

6p

2

, 6p

3

, and 6p

4

 ground configurations of neutral Pb, Bi, and Po, respectively; the notations for

the ground levels of these atoms are given as the first three examples above. The configuration in the

first example shows the notation for equivalent electrons having the same j value l

j

N, in this case two

6p electrons each having j = 1/

2

. A convenient notation for a particular level (J = 0) of such a group

is also indicated. The second example extends this notation to the case of a 6p

3

 configuration

divided into two groups according to the two possible j values. A similar notation is shown for the

6p

4

 level in the third example; this level might also be designated (6p

-2

3/2)2

, the negative

superscript indicating the two 6p holes. The (J

1

, J

2

)

J

 term and level notation shown on the right in

the fourth example is convenient because each of the two electron groups 4d

3

5/2 and 4d

2

3/2 has

more than one allowed total J

i

 value. The assumed convention is that J

1

 applies to the group on the

left (J

1

 = 9/

2

 for the 4d

3

5/2 group) and J2

 to that on the right. 

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Atomic Spectroscopy: An Introduction
J1

 j or J1J2 Coupling

1. 3d

9

(

2D5/2)4p

3/2 (5

/

2

, 

3

/

2

)°3

2. 4f

11(2H°9/2 2)6s6p(3P°1

) (9/

2

, 1)7/2

3. 4f

9

(

6H°)5d (7H°8

)6s6p(

3P°0

) (8,0)8

4. 4f

12(3H6

) 5d(

2D)6s6p(3P°) (4F°3/2) (6, 3

/

2

)°13/2

5. 5f

4

(

5

I

4

)6d3/2 (4,3/

2

)

11/27s7p(

1P°1

) (11/

2

, 1)°9/2

6. 5f

4

7/25f

5

5/2 (8,5

/

2

)°21/27p

3/2 (21/2

, 

3

/

2

)

10

7. 5f

3

7/2 5f

3

5/2 (9

/

2

, 

9

/

2

)

9

7s7p(

3P°2

) (9,2)°7

The first five examples all have core electrons in LS coupling, whereas jj coupling is indicated for the

5f core electrons in the last two examples. Since the J

1

 and J

2

 values in the final (J

1

, J

2

) term have

already been given as subscripts in the configuration, the (J

1

, J

2

) term notations are redundant in all

these examples. Unless separation of the configuration and final term designations is desired, as in

some data tables, one may obtain a more concise notation by simply enclosing the entire

configuration in brackets and adding the final J value as a subscript. Thus, the level in the first

example can be designated as [3d

9

(

2D5/2) 4p3/2]°3

. If the configuration and coupling order are

assumed to be known, still shorter designations may be used; for example, the fourth level above

might then be given as [(3H6) (3P°) (4F°3/2)]13/2 or (3H6, 

3P°, 4F°3/2)

13/2. Similar economies of

notation are of course possible, and often useful, in all coupling schemes. 

J1l or J1L2 Coupling (J1K Coupling)

1. 3p

5

(

2P°1/2)5g 2

[

9

/

2

]°5

2. 4f

2

(

3H4

)5g 

2

[3]5/2

3. 4f

13(2F°7/2)5d2

(

1D) 1

[

7

/

2

]°7/2

4. 4f

13(2F°5/2)5d6s(3D) 3

[

9

/

2

]°11/2

The final terms in the first two examples result from coupling a parent-level J

1

 to the orbital angular

momentum of a 5g electron to obtain a resultant K, the K value being enclosed in brackets. The spin

of the external electron is then coupled with the K angular momentum to obtain a pair of J values,

J = K ± 1/

2

 (for K 0). The multiplicity (2) of such pair terms is usually omitted from the term

symbol, but other multiplicities occur in the more general J

1

L2 coupling (examples 3 and 4). The last

two examples are straightforward extensions of J

1

l coupling, with the L2 and S2 momenta of the

"external"' term (1D and 3D in examples 3 and 4, respectively) replacing the l and s momenta of a

single external electron. 

LS1 Coupling (LK Coupling)

11 of 31 3/3/1999 8:09 AM

Atomic Spectroscopy: An Introduction
1. 3s

23p(2P°)4f G 2

[

7

/

2

]

3

2. 3d

7

(

4P)4s4p(3P°) D° 3

[

5

/

2

]°7/2

The orbital angular momentum of the core is coupled with the orbital angular momentum of the

external electron(s) to give the total orbital angular momentum L. The letter symbol for the final L

value is listed with the configuration because this angular momentum is then coupled with the spin of

the core (S1) to obtain the resultant K angular momentum of the final term (in brackets). The

multiplicity of the [K] term arises from the spin of the external electron(s). 

Coupling Schemes and Term Symbols

The coupling schemes outlined above include those now most frequently used in calculations of

atomic structure [3]. Any term symbol gives the values of two angular momenta that may be

coupled to give the total electronic angular momentum of a level (indicated by the J value). For

configurations of more than one unfilled subshell, the angular momenta involved in the final coupling

derive from two groups of electrons (either group may consist of only one electron). These are often

an inner group of coupled electrons and an outer group of coupled electrons, respectively. In any

case the quantum numbers for the two groups can be distinguished by subscripts 1 and 2, so that

quantum numbers represented by capital letters without subscripts are total quantum numbers for

both groups. Thus, the quantum numbers for the two vectors that couple to give the final J are

related to the term symbol as follows: 

Coupling

Scheme

Quantum numbers for vectors

that couple to give J

Term

Symbol

LS L,S 2S+1L

J

1

J

2

J

1

, J

2

(J

1

, J

2

)

J

1

L2( K) K, S2

2S2+1[K]

LS1( K) K, S2

2S2+1[K]

The parity is indicated by appended degree symbols on odd parity terms. 

 

10. EIGENVECTOR COMPOSITION OF LEVELS

The wave functions of levels are often expressed as eigenvectors that are linear combinations of basis

states in one of the standard coupling schemes. Thus, the wave function ( J) for a level labeled J might

be expressed in terms of normalized LS coupling basis states ( SLJ): 

12 of 31 3/3/1999 8:09 AM

Atomic Spectroscopy: An Introduction
(4)

The c( SLJ) are expansion coefficients, and 

(5)

The squared expansion coefficients for the various SL terms in the composition of the J level are

conveniently expressed as percentages, whose sum is 100%. Thus the percentage contributed by the pure

Russell-Saunders state SLJ is equal to 100 x |c( SLJ)|2. The notation for Russell-Saunders basis states

has been used only for concreteness; the eigenvectors may be expressed in any coupling scheme, and the

coupling schemes may be different for different configurations included in a single calculation (with

configuration interaction). "Intermediate coupling" conditions for a configuration are such that

calculations in both LS and jj coupling yield some eigenvectors representing significant mixtures of basis

states. 

The largest percentage in the composition of a level is called the purity of the level in that coupling

scheme. The coupling scheme (or combination of coupling schemes if more than one configuration is

involved) that results in the largest average purity for all the levels in a calculation is usually best for

naming the levels. With regard to any particular calculation, one does well to remember that, as with

other calculated quantities, the resulting eigenvectors depend on a specific theoretical model and are

subject to the inaccuracies of whatever approximations the model involves. 

Theoretical calculations of experimental energy level structures have yielded many eigenvectors having

significantly less than 50% purity in any coupling scheme. Since many of the corresponding levels have

nevertheless been assigned names by spectroscopists, some caution is advisable in the acceptance of level

designations found in the literature. 

11. GROUND LEVELS AND IONIZATION ENERGIES FOR

THE NEUTRAL ATOMS

Table of Ground Levels and Ionization Energies for the Neutral Atoms

When using the above table, be sure to use your "Back" button to return to this document.

The ground-state electron configurations of elements heavier than neon are shortened in the table by

using rare-gas element symbols in brackets to represent the corresponding electrons. The ground levels of

all neutral atoms have reasonably meaningful LS-coupling names, the corresponding eigenvector

percentages lying in the range from ~55 % to 100 %. These names are listed in the table, except for Pa,

U, and Np; the lowest few ground-configuration levels of these atoms comprise better 5f N(L1S

1

J

1

),

6d

j

7s

2

 (J

1

j) terms than LS-coupling terms. The relatively large spin-orbit interaction of the 6p electrons

produces jj-coupling structures for the (6p

2

1/2)0

, (6p

2

1/26p3/2)

o

3/2, and (6p

2

1/26p

2

3/2)2

 ground levels of

the 6p

2

, 6p

3

, and 6p

4

 configurations of neutral Pb, Bi, and Po, respectively. As noted in the section jj

Coupling of Equivalent Electrons, the jj-coupling names are more appropriate for these atoms than the

alternative LS-coupling designations in the table. 

The ionization energies in the table are based on a recent survey of the literature [13]. The uncertainties

13 of 31 3/3/1999 8:09 AM

Atomic Spectroscopy: An Introduction
are mainly in the range from less than one to several units in the last decimal place, but a few of the values

may be in error by 20 or more units in the final place; i.e., the error of some of the two place values could

be greater than 0.2 eV. Estimated uncertainties of the ionization energies are usually given in the

references. Although no more than four decimal places are given, the accuracies of some of the better

known values would, in eV units, be limited only by the uncertainty in the conversion factor,

1.239 842 44(37) x 10-4 eV/cm-1.

12. ZEEMAN EFFECT

The Zeeman effect for "weak" magnetic fields (the anomalous Zeeman effect) is of special interest

because of the importance of Zeeman data in the analysis and theoretical interpretation of complex

spectra. In a weak field, the J value remains a good quantum number although in general a level is split

into magnetic sublevels [3]. The g value of such a level may be defined by the expression for the energy

shift of its magnetic sublevel having magnetic quantum number M, which has one of the 2J + 1 values, -J,

-J + 1, ..., J: 

E = gM μBB . (6)

The magnetic flux density is B, and μB is the Bohr magneton (μB = e /2me). 

The wavenumber shift corresponding to this energy shift is 

 = gM(0.466 86 B cm-1) , (7)

with B representing the numerical value of the magnetic flux density in teslas. The quantity in

parentheses, the Lorentz unit, is of the order of 1 or 2 cm-1 for typical flux densities used to obtain

Zeeman-effect data with classical spectroscopic methods. Accurate data can be obtained with much

smaller fields, of course, by using higher-resolution techniques such as laser spectroscopy. Most of the g

values now available for atomic energy levels were derived by application of the above formula (for each

of the two combining levels) to measurements of optical Zeeman patterns. A single

transverse-Zeeman-effect pattern (two polarizations, resolved components, and sufficiently complete) can

yield the J value and the g value for each of the two levels involved. 

Neglecting a number of higher-order effects, we can evaluate the g value of a level J belonging to a pure

LS-coupling term using the formula 

(8)

The independence of this expression from any other quantum numbers (represented by ) such as the

configuration, etc., is important. The expression is derived from vector coupling formulas by assuming a

g value of unity for a pure orbital angular momentum and writing the g value for a pure electron spin as

g

e

[14]. A value of 2 for g

e

 yields the Landé formula. If the anomalous magnetic moment of the electron

is taken into account, the value of g

e

 is 2.002 319 3. "Schwinger" g values obtained with this more

accurate value for g

e

 are given for levels of SL terms in Ref. [8]. 

14 of 31 3/3/1999 8:09 AM

Atomic Spectroscopy: An Introduction
The usefulness of g

SLJ values is enhanced by their relation to the g values in intermediate coupling. In the

notation used in Eq. (4) for the wave function of a level J in intermediate coupling, the corresponding g

value is given by 

(9)

where the summation is over the same set of quantum numbers as for the wave function. The g

J

 value is

thus a weighted average of the Landé g

SLJ values, the weighting factors being just the corresponding

component percentages. 

Formulas for magnetic splitting factors in the J

1

J

2

 and J

1

L2 coupling schemes are given in Refs. [8]] and

[14]. Some higher-order effects that must be included in more accurate Zeeman-effect calculations are

treated by Bethe and Salpeter [4] and by Wybourne [14], for example. High precision calculations for

helium are given in Ref. [15]. 

13. TERM SERIES, QUANTUM DEFECTS, AND

SPECTRAL-LINE SERIES

The Bohr energy levels for hydrogen or for a hydrogenic (one-electron) ion are given by 

(10)

in units of RM, the Rydberg for the appropriate nuclear mass. For a multielectron atom, the deviations of

a series of (core)nl levels from hydrogenic En values may be due mainly to core penetration by the nl

electron (low l-value series), or core polarization by the nl electron (high l-value series), or a combination

of the two effects. In either case it can be shown that these deviations can be approximately represented

by a constant quantum defect l in the Rydberg formula, 

(11)

where Zc is the charge of the core and n* = n - is the effective principal quantum number. If the core

includes only closed subshells, the Enl values are with respect to a value of zero for the (core)1S0 level,

i.e., the 1S0 level is the limit of the (core)nl series. If the quantities in Eq. (11) are taken as positive, they

represent term values or ionization energies; the term value of the ground level of an atom or ion with

respect to the ground level of the next higher ion is thus the principal ionization energy. 

If the core has one or more open subshells, the series limit may be the baricenter of the entire core

configuration, or any appropriate sub-structure of the core, down to and including a single level. The Enl

values refer to the series of corresponding (core)nl structures built on the particular limit structure. The

value of the quantum defect depends to some extent on which (core)nl structures are represented by the

series formula. 

The quantum defect in general also has an energy dependence that must be taken into account if lower

members of a series are to be accurately represented by Eq. (11). For an unperturbed series, this

15 of 31 3/3/1999 8:09 AM

Atomic Spectroscopy: An Introduction
dependence can be expressed by the extended Ritz formula 

(12)

 

with 0,a,b... constants for the series ( 0 being the limit value of the quantum defect for high series

members) [16]. The value of a is usually positive for core-penetration series and negative for

core-polarization series. A discussion of the foundations of the Ritz expansion and application to high

precision calculations in helium is given in Ref. [17]. 

A spectral-line series results from either emission or absorption transitions involving a common lower

level and a series of successive (core)nl upper levels differing only in their n values. The principal series

of Na I, 3s

2S1/2 - np 2P°1/2,3/2 (n 3) is an example. The regularity of successive upper term values with

increasing n [Eqs. (11), (12)] is of course observed in line series; the intervals between successive lines

decrease in a regular manner towards higher wavenumbers, and the series of increasing wavenumbers

converges towards the term value of the lower level as a limit. 

14. SEQUENCES

Several types of sequences of elements and/or ionization stages are useful because of regularities in the

progressive values of parameters relating to structure and other properties along the sequences. All

sequence names may refer either to the atoms and/or ions of the sequence or to their spectra. 

Isoelectronic Sequence

A neutral atom and those ions of other elements having the same number of electrons as the atom

comprise an isoelectronic sequence. (Note that a negative ion having this number of electrons is a

member of the sequence.) An isoelectronic sequence is named according to its neutral member; for

example, the Na I isolectronic sequence. 

Isoionic, Isonuclear, and Homologous Sequences

An isoionic sequence comprises atoms or ions of different elements having the same charge. Such

sequences have probably been most useful along the d- and f-shell rows of the periodic table.

Isoionic analyses have also been carried out along p-shell rows, however, and a fine-structure

regularity covering spectra of the p-shell atoms throughout the periodic table is known [18]. 

The atom and successive ions of a particular element comprise the isonuclear sequence for that

element. 

The elements of a particular column and subgroup in the periodic table are homologous. Thus the C,

Si, Ge, Sn, and Pb atoms belong to a homologous sequence having np2 ground configurations (see

Table of Ground Levels and Ionization Energies for the Neutral Atoms). The singly ionized atoms of

16 of 31 3/3/1999 8:09 AM

Atomic Spectroscopy: An Introduction
these elements comprise another example of a homologous sequence. 

15. SPECTRAL WAVELENGTH RANGES, DISPERSION OF

AIR

The ranges of most interest for optical atomic spectroscopy are: 

~ 2 - 20 μm mid-infrared (ir)

700 - 2000 nm near ir

400 - 700 nm visible

200 - 400 nm near ultraviolet (uv)

100 - 200 nm vacuum uv or far uv

10 - 100 nm extreme uv (euv or xuv)

< 10 nm soft x-ray, x-ray

The above correspondence of names to ranges should not be taken as exact; the variation as to the extent

of some of the named ranges found in the literature is considerable. 

Wavelengths in standard air are often tabulated for the region longer than 200 nm. These wavelengths can

be related to energy-level differences by conversion to the corresponding (vacuum) wavenumbers or

frequencies [19].

16. WAVELENGTH (FREQUENCY) STANDARDS

In 1992 the Comité International des Poids et Mesures recommended values for six frequencies for the

absorbing molecule 127I

2

 (515 nm to 640 nm), one frequency for the 40Ca atom (657 nm), and one for

methane (3.39 μm) as standards for suitably stabilized lasers [20]. These frequencies range from

88 376 181.600 18 MHz (3.392 231 397 327 μm, fractional uncertainty 3 x 10-12) for a particular

hyperfine-structure (hfs) component in methane to 582 490 603.37 MHz (514.673 466 4 nm, fractional

uncertainty 2.5 x 10-10) for a particular hfs component in 127I

2

. Reference [20] also gives accurate values

for hfs frequency intervals in 127I

2

 that connect each of the six standard frequencies to other hfs

components of the same or nearby transitions. 

Extensive tables of wavenumbers for molecular transitions in the mid-ir range 2.3 μm to 20.5 μm are

included in a calibration atlas published in 1991 [21]. Measurements of U and Th lines (575 to 692 nm)

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Atomic Spectroscopy: An Introduction
suitable for wavenumber calibration at uncertainty levels of 0.0003 cm-1 or 0.0004 cm-1 were reported in

Ref. [22]. Comprehensive tables of lines for U [23], Th [24], and I2[25] are useful for calibration at

uncertainty levels of 0.002 cm-1 to 0.003 cm-1, the atlas of the Th spectrum extending down to 278 nm. 

A 1974 compilation gives reference wavelengths for some 5400 lines of 38 elements covering the range

1.5 nm to 2.5 μm, with most uncertainties between 10-5 and 2 x 10-4 nm [26]. Norlén's tables of Ar I and

Ar II wavelengths range from 156 nm to 2.4 μm, with uncertainties of 1 to 3 x 10-5 nm for the more

accurate wavelengths shorter than ~ 850 nm [27]. The wavelengths for some 1100 Fe lines selected from

the Fe/Ne hollow-cathode spectrum have been recommended for reference standards over the range

183 nm to 4.2 μm, with wavenumber uncertainties 0.001 cm-1 to 0.002 cm-1 [28]. Wavelengths for about

3000 vuv and uv lines (110 to 400 nm) from a Pt/Ne hollow-cathode lamp have been determined with

uncertainties of 0.0002 nm or less [29]. 

17. SPECTRAL LINES: SELECTION RULES, INTENSITIES,

TRANSITION PROBABILITIES, VALUES, AND LINE

STRENGTHS 

Selection rules for discrete transitions.

 Electric dipole (E1) 

("allowed")

 Magnetic dipole (M1) 

("forbidden")

 Electric quadrupole (E2)

("forbidden")

Rigorous rules 1. J = 0, ± 1

(except 0 0)

J = 0, ± 1

(except 0 0)

J = 0, ± 1, ± 2

(except 0 0,

1/2 1/2, 0 1)

2. M = 0, ± 1

(except 0 0

when J = 0)

M = 0, ± 1

(except 0 0

when J = 0)

M = 0, ± 1, ± 2

3. Parity change No parity change No parity change

With negligible 

configuration

interaction

4. One electron

jumping, with

l = ± 1,

n arbitrary

No change in electron

configuration; i.e., for 

all electrons, l = 0,

n = 0

No change in electron

configuration; or one

electron jumping with

l = 0, ± 2, n arbitrary

For LS

coupling only

5. S = 0 S = 0 S = 0

6. L = 0, ± 1

(except 0 0)

L = 0

J = ± 1

L = 0, ± 1, ± 2

(except 0 0, 0 1)

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Atomic Spectroscopy: An Introduction
Emission Intensities (Transition Probabilities)

The total power radiated in a spectral line of frequency per unit source volume and per unit solid

angle is 

line = (4 )

-1 h Aki Nk

 , (13)

where Aki is the atomic transition probability and Nk the number per unit volume (number density) of

excited atoms in the upper (initial) level k. For a homogeneous light source of length l and for the

optically thin case, where all radiation escapes, the total emitted line intensity (SI quantity: radiance)

is 

(14)

where I( ) is the specific intensity at wavelength , and 0 the wavelength at line center.

Absorption f values

In absorption, the reduced absorption

W( ) = [I( ) - I ( )]/I( ) (15)

is used, where I( ) is the incident intensity at wavelength , e.g., from a source providing a

continuous background, and I ( ) the intensity after passage through the absorbing medium. The

reduced line intensity from a homogeneous and optically thin absorbing medium of length l follows

as 

(16)

where f

ik is the atomic (absorption) oscillator strength (dimensionless).

Line Strengths

Aki and f

ik are the principal atomic quantities related to line intensities. In theoretical work, the line

strength S is also widely used (see Atomic, Molecular, & Optical Physics Handbook, Chap. 21, ed.

by G.W.F. Drake (AIP, Woodbury, NY, 1996): 

19 of 31 3/3/1999 8:09 AM

Atomic Spectroscopy: An Introduction
S = S(i,k) = S(k,i) = | Rik | 2

 , (17)

Rik = < k | P | i> , (18)

where i and k are the initial- and final-state wave functions and Rik is the transition matrix

element of the appropriate multipole operator P (Rik involves an integration over spatial and spin

coordinates of all N electrons of the atom or ion).

Relationships between A, f, and S

The relationships between A, f, and S for electric dipole (E1, or allowed) transitions in SI units (A in

s

-1

, in m, S in m2 C2) are 

 

(19)

Numerically, in customary units (A in s-1, in Å, S in atomic units), 

(20)

and for S and E in atomic units,

(21)

g

i

 and g

k

 are the statistical weights, which are obtained from the appropriate angular momentum

quantum numbers. Thus for the lower (upper) level of a spectral line, g

i(k)

 = 2J

i(k)

 + 1, and for the

lower (upper) term of a multiplet, 

(22)

The Aki values for strong lines of selected elements are given. For comprehensive numerical tables of

A, f, and S, including forbidden lines (see Sources of Spectroscopic Data). 

Experimental and theoretical methods to determine A, f, or S values as well as atomic lifetimes are

discussed in Atomic, Molecular, & Optical Physics Handbook, Chaps. 17, 18, and 21, ed. by

G.W.F. Drake (AIP, Woodbury, NY, 1996). 

Conversion relations between S and Aki for the most common forbidden transitions

20 of 31 3/3/1999 8:09 AM

Atomic Spectroscopy: An Introduction
SI unitsa

Numerically, in

customary unitsb

Electric quadrupole 

Magnetic dipole 

aA in s-1

, in m. Electric quadrupole: S in m4 C2. Magnetic dipole: S in J2 T-2.

bA in s-1

, in Å. S in atomic units: = 2.013 x 10-79 m4 C2 (electric

quadrupole), = 8.601 x 10-47 J2 T-2 (magnetic dipole). μB is

the Bohr magneton. 

Oscillator strengths f are not used for forbidden transitions, i.e., magnetic dipole (M1), electric

quadrupole (E2), etc. 

[Numerical example: For the 1s2p

1P - 1s3d1D2

 (allowed) transition in He I at 6678.15 Å: g

i

 = 3;

g

k

 = 5; Aki = 6.38 x 107 s-1; f

ik = 0.711; S = 46.9 a0

2

e

2

.]

Relationships between Line and Multiplet Values

The relations between the total strength and f value of a multiplet (M) and the corresponding

quantities for the lines of the multiplet (allowed transitions) are 

(23)

(24)

 is the weighted ("multiplet") wavelength in vacuum: 

(25)

where 

(26)

and n is the refractive index of standard air.

Relative Strengths for Lines of Multiplets in LS Coupling

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Atomic Spectroscopy: An Introduction
This table lists relative line strengths for frequently encountered symmetrical (P P, D D) and

normal (S P, P D) multiplets in LS coupling. The strongest, or principal, lines are situated along

the main diagonal of the table and are called x

1

, x

2

, etc. Their strengths normally diminish along the

diagonal. The satellite lines y

n

 and z

n

 are usually weaker and deviate more from the LS values than

the stronger diagonal lines when departures from LS coupling are encountered. The total multiplet

strengths SM are also listed in this table. A discussion of their normalization as well as more

extensive tables are given in Ref. [30]. 

Relative Strengths for Lines of Multiplets in LS Coupling

Normal multiplets S - P, P - D, D - F, etc. Symmetrical multiplets P - P, D - D, etc.

JmJm - 1 Jm - 2 Jm - 3 Jm - 4 JmJm - 1 Jm - 2 Jm - 3

Jm - 1 x

1

y

1

z

1

 Jm x

1

y

1

 

Jm - 2 x

2

y

2

z

2

Jm - 1 y

1

x

2

y

2

 

Jm - 3 x

3

y

3

z

3

Jm - 2 y

2

x

3

y

3

Jm - 4 x

4

y

4

Jm - 3 y

3

x

4

Multiplicity Multiplicity

1 2 3 4 5 1 2 3 4 5

S - P D - D

SM = 3 6 9 12 15 SM = 25 50 75 100 125

x

1

3.00 4.00 5.00 6.00 7.00 x

1

25.00 28.00 31.11 34.29 37.50

y

1

2.00 3.00 4.00 5.00 x

2

18.00 17.36 17.29 17.50

z

1

 1.00 2.00 3.00 x

3

 11.25 8.00 6.25

x

4

 5.00 1.25

P - P

SM = 9 18 27 36 45 y

1

2.00 3.89 5.71 7.50

y

2

 3.75 7.00 10.00

x

1

9.00 10.00 11.25 12.60 14.00 y

3

 5.00 8.75

x

2

4.00 2.25 1.60 1.25 y

4

 5.00

x

3

 1.00 2.25

D - F

y

1

2.00 3.75 5.40 7.00 SM = 35 70 105 140 175

y

2

 3.00 5.00 6.75

x

1

35.00 40.00 45.00 50.00 55.00

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Atomic Spectroscopy: An Introduction
P - D x

2

28.00 31.11 34.29 37.50

SM = 15 30 45 60 75 x

3

 21.00 22.40 24.00

x

4

 14.00 14.00

x

1

15.00 18.00 21.00 24.00 27.00 x

5

 7.00

x

2

10.00 11.25 12.60 14.00

x

3

 5.00 5.00 5.25 y

1

2.00 3.89 5.71 7.50

y

2

 3.89 7.31 10.50

y

1

2.00 3.75 5.40 7.00 y

3

 5.60 10.00

y

2

 3.75 6.40 8.75 y

4

 7.00

y

3

 5.60 6.75

z

1

 .11 .29 .50

z

1

 .25 .60 1.00 z

2

 .40 1.00

z

2

 1.00 2.25 z

3

 1.00

z

3

 3.00

18. ATOMIC LIFETIMES

The radiative lifetime k of an atomic level k is related to the sum of transition probabilities to all levels i

lower in energy than k: 

 

(27)

The branching ratio of a particular transition, say to state i , is defined as 

 

(28)

If only one branch (i ) exists (or if all other branches may be neglected), one obtains Aki k = 1, and 

 k

 = 1/Aki . (29)

Precision lifetime measurement techniques are discussed in Atomic, Molecular, & Optical Physics

Handbook, Chaps. 17 and 18, ed. by G.W.F. Drake (AIP, Woodbury, NY, 1996). 

19. REGULARITIES AND SCALING

 

Transitions in Hydrogenic (One-Electron) Species

The nonrelativistic energy of a hydrogenic transition [Eqs. (1), (10)] is 

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Atomic Spectroscopy: An Introduction
(30)

Hydrogenic Z scaling. The spectroscopic quantities for a hydrogenic ion of nuclear charge Z are

related to the equivalent quantities in hydrogen (Z = 1) as follows (neglecting small differences in the

values of RM): 

( E)

Z

 = Z

2

( E)H , (31)

(

vac)Z

 = Z

-2(

vac)H

 , (32)

S

Z

 = Z

-2 SH

 , (33)

f

Z

 = fH , (34)

AZ = Z

4 AH

 , (35)

For large values of Z, roughly Z > 20, relativistic corrections become noticeable and must be taken

into account. 

f-value trends. f values for high series members (large n values) of hydrogenic ions decrease

according to 

f(n,l n , l ± 1) (n )

-3

 . (36)

Data for some lines of the main spectral series of hydrogen are given in the table below. 

Some transitions of the main spectral series of hydrogen

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Atomic Spectroscopy: An Introduction
TransitionCustomary

namea

b

(Å) g

i

c

 g

k

Aki

(108 s-1)

1-2 (L ) 1 215.67

 

2

 

8

 

4.699

1-3 (L ) 1 025.73 2 18 5.575(-1)d

1-4 (L ) 972.537 2 32 1.278(-1)

1-5 (L ) 949.743 2 50 4.125(-2)

1-6 (L ) 937.80 2 72 1.644(-2)

2-3 (H ) 6 562.80 8 18 4.410(-1)

2-4 (H ) 4 861.32 8 32 8.419(-2)

2-5 (H ) 4 340.46 8 50 2.530(-2)

2-6 (H ) 4 101.73 8 72 9.732(-3)

2-7 (H ) 3 970.07 8 98 4.389(-3)

3-4 (P ) 18 751.0 18 32 8.986(-2)

3-5 (P ) 12 818.1 18 50 2.201(-2)

3-6 (P ) 10 938.1 18 72 7.783(-3)

3-7 (P ) 10 049.4 18 98 3.358(-3)

3-8 (P ) 9 545.97 18 128 1.651(-3)

aL is often called Lyman , H = Balmer , P = Paschen , etc.

bWavelengths below 2000 Å are in vacuum; values above 2000 Å are in air.

cFor transitions in hydrogen, gi(k)

 = 2(ni(k)

)

2

, where ni(k)

, is the principal quantum

number of the lower (upper) electron shell. 

dThe number in parentheses indicates the power of 10 by which the value has to be

multiplied.

Systematic Trends and Regularities in Atoms and Ions with

Two or More Electrons

Nonrelativistic atomic quantities for a given state or transition in an isoelectronic sequence may be

expressed as power series expansions in Z

-1: 

Z

-2 E = E0

 + E1Z

-1 + E2

Z

-2 + ... , (37)

 Z

2 S = S

0

 + S

1

Z

-1 + S

2

Z

-2 + ... , (38)

 f = f

0

 + f

1

Z

-1 + f

2

Z

-2 + ... , (39)

where E0, f

0

, and S0 are hydrogenic quantities. For transitions in which n does not change (n

i

 = n

k

),

f

0

 = 0, since states i and k are degenerate. 

For equivalent transitions of homologous atoms, f values vary gradually. Transitions to be compared

in the case of the "alkalis" are [31] 

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Atomic Spectroscopy: An Introduction
Complex atomic structures, as well as cases involving strong cancellation in the integrand of the

transition integral, generally do not adhere to this regular behavior. 

20. SPECTRAL LINE SHAPES, WIDTHS, AND SHIFTS

Observed spectral lines are always broadened, partly due to the finite resolution of the spectrometer and

partly due to intrinsic physical causes. The principal physical causes of spectral line broadening are

Doppler and pressure broadening. The theoretical foundations of line broadening are discussed in Atomic,

Molecular, & Optical Physics Handbook, Chaps. 19 and 57, ed. G.W.F. Drake (AIP, Woodbury, NY,

1996). 

Doppler Broadening

Doppler broadening is due to the thermal motion of the emitting atoms or ions. For a Maxwellian

velocity distribution, the line shape is Gaussian; the full width at half maximum intensity (FWHM)

is, in Å, 

(40)

T is the temperature of the emitters in K, and M the atomic weight in atomic mass units (amu).

Pressure Broadening

Pressure broadening is due to collisions of the emitters with neighboring particles [see also Atomic,

Molecular, & Optical Physics Handbook, Chaps. 19 and 57, ed. G.W.F. Drake (AIP, Woodbury,

NY, 1996)]. Shapes are often approximately Lorentzian, i.e., . In the

following formulas, all FWHM's and wavelengths are expressed in Å, particle densities N in cm-3,

temperatures T in K, and energies E or I in cm-1. 

Resonance broadening (self-broadening) occurs only between identical species and is confined to

lines with the upper or lower level having an electric dipole transition (resonance line) to the ground

state. The FWHM may be estimated as 

(41)

where is the wavelength of the observed line. f

r

 and 

r

 are the oscillator strength and wavelength

of the resonance line; g

k

 and g

i

 are the statistical weights of its upper and lower levels. Ni is the

ground state number density. 

For the 1s2p

1P - 1s3d 1D2

 transition in He I [ = 6678.15 Å; r (1s

2

 

1S0

 - 1s2p

1P ) =

584.334 Å; g

i

 = 1; g

k

 = 3; f

r

 = 0.2762] at Ni = 1 x 1018 cm-3: R

1/2 = 0.036 Å. 

Van der Waals broadening arises from the dipole interaction of an excited atom with the induced

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Atomic Spectroscopy: An Introduction
dipole of a ground state atom. (In the case of foreign gas broadening, both the perturber and the

radiator may be in their respective ground states.) An approximate formula for the FWHM, strictly

applicable to hydrogen and similar atomic structures only, is 

(42)

where μ is the atom-perturber reduced mass in units of u, N the perturber density, and C6 the

interaction constant. C6 may be roughly estimated as follows: C6 = Ck - Ci, with Ci (k) = (9.8 x 1010)

(

d

R

2

i

(k) d in cm3, R

2

 in a

0

2

). Mean atomic polarizability d (6.7 x 10-25) (3IH/4E*)2 cm3,

where IH is the ionization energy of hydrogen and E* the energy of the first excited level of the

perturber atom. R

2

i (k)

 2.5 [IH/(I-Ei (k))]2, where I is the ionization energy of the radiator. Van der

Waals broadened lines are red shifted by about one-third the size of the FWHM. 

For the 1s2p

1P - 1s3d1D2

 transition in He I, and with He as perturber: = 6678.15 Å;

I = 198 311 cm-1; E

*

 = Ei = 171 135 cm-1; Ek = 186 105 cm-1; μ = 2. At T = 15 000 K and

N = 1 × 1018 cm-3: W

1/2 = 0.044 Å. 

Stark broadening due to charged perturbers, i.e., ions and electrons, usually dominates resonance

and van der Waals broadening in discharges and plasmas. The FWHM for hydrogen lines is 

(43)

where Ne is the electron density. The half-width parameter 1/2 for the H line at 4861 Å, widely

used for plasma diagnostics, is tabulated in the table below for some typical temperatures and

electron densities [30]. This reference also contains 1/2 parameters for other hydrogen lines, as well

as Stark width and shift data for numerous lines of other elements, i.e., neutral atoms and singly

charged ions (in the latter, Stark widths and shifts depend linearly on Ne). Other tabulations of

complete hydrogen Stark profiles exist. 

Values of Stark-broadening parameter 1/2 for the H line of hydrogen (4861 Å)

for various temperatures and electron densities.

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Atomic Spectroscopy: An Introduction
Ne

 (cm-3)

T(K) 1015 1016 1017 1018

5 000 0.0787 0.0808 0.0765 ...

10 000 0.0803 0.0840 0.0851 0.0781

20 000 0.0815 0.0860 0.0902 0.0896

30 000 0.0814 0.0860 0.0919 0.0946

21. SPECTRAL CONTINUUM RADIATION

Hydrogenic Species

Precise quantum-mechanical calculations exist only for hydrogenic species. The total power cont

radiated (per unit source volume and per unit solid angle, and expressed in SI units) in the

wavelength interval is the sum of radiation due to the recombination of a free electron with a

bare ion (free-bound transitions) and bremsstrahlung (free-free transitions): 

cont = 

(44)

where Ne is the electron density, NZ the number density of hydrogenic (bare) ions of nuclear charge

Z, IH the ionization energy of hydrogen, n the principal quantum number of the lowest level for

which adjacent levels are so close that they approach a continuum and summation over n may be

replaced by an integral. (The choice of n is rather arbitrary; n as low as 6 is found in the literature.)

f b

 and ff are the Gaunt factors, which are generally close to unity. (For the higher free-bound

continua, starting with n + 1, an average Gaunt factor f b is used.) For neutral hydrogen, the

recombination continuum forming H

-

 becomes important, too [32]. 

In the equation above, the value of the constant factor is 6.065 x 10-55 W m4 J1/2 sr-1. [Numerical

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Atomic Spectroscopy: An Introduction
example: For atomic hydrogen (Z = 1), the quantity cont has the value 2.9 W m-3 sr-1 under the

following conditions: = 3 x 10-7 m; = 1 x 10-10 m; Ne (= NZ=1) = 1 x 1021 m-3; T = 12 000 K.

The lower limit of the summation index n is 2; the upper limit n has been taken to be 10. All Gaunt

factors f b, f b, ff have been assumed to be unity.]

Many-Electron Systems

For many-electron systems, only approximate theoretical treatments exist, based on the

quantum-defect method (for results of calculations for noble gases, see, e.g., Ref. [33]).

Experimental work is centered on the noble gases [34]. Modifications of the continuum by

autoionization processes must also be considered. 

Near the ionization limit, the f values for bound-bound transitions of a spectral series (n )

make a smooth connection to the differential oscillator strength distribution df/d in the continuum

[35]. 

22. SOURCES OF SPECTROSCOPIC DATA

A few data compilations have been cited above [8], [12], [30], and Wavelength (Frequency) Standards

includes additional references for wavelength tables. A compilation of energy levels and other

spectroscopic data for the actinide elements is also available [36]. Major recent compilations of atomic

transition probabilities cover C, N and O [37] and the Fe-group elements [38]. A fairly comprehensive

bibliographic review of compilations of data on atomic energy levels, wavelengths, transition

probabilities, and spectral line shapes and shifts was published in 1992 [39]. Extensive data from

compilations and other sources, as well as bibliographies, are included in the holdings of the NIST

Atomic Spectra Database.

23. REFERENCES

1 The International System of Units (SI), edited by B. N. Taylor NIST Spec. Publ. 330 (U. S.

Government Printing Office, Washington, 1991), p. 29. 

2 E. U. Condon and G. H. Shortley, The Theory of Atomic Spectra (Cambridge University Press,

Cambridge, 1935, reprinted 1951). 

3 R. D. Cowan, The Theory of Atomic Structure and Spectra (University of California Press,

Berkeley, 1981). 

4 H. A. Bethe and E. E. Salpeter, Quantum Mechanics of One- and Two-Electron Atoms (Plenum,

New York, 1977). 

5 B. Edlén, in Encyclopedia of Physics, edited by S. Flügge (Springer-Verlag, Berlin, 1964). Vol. 27. 

29 of 31 3/3/1999 8:09 AM

Atomic Spectroscopy: An Introduction
6 H. N. Russell and F. A. Saunders, Astrophys. J. 61, 38 (1925). 

7 C. W. Nielson and G. F. Koster, Spectroscopic Coefficients for the p

n

, d

n

, and f

n

 Configurations

(MIT Press, Cambridge, 1963). 

8 W. C. Martin, R. Zalubas, and L. Hagan, Atomic Energy Levels -- The Rare-Earth Elements, Nat.

Stand. Ref. Data Ser., Nat. Bur. Stand. (United States Government Printing Office, Washington,

1978), No. 60. 

9 A. de-Shalit and I. Talmi, Nuclear Shell Theory (Academic, New York, 1963). 

10 H. N. Russell, A. G. Shenstone, and L. A. Turner, Phys. Rev. 33, 900 (1929). 

11 R. F. Bacher and S. Goudsmit, Atomic Energy States (McGraw-Hill, New York, 1932). 

12 C. E. Moore, Atomic Energy Levels, Nat. Stand. Ref. Data Ser., Nat. Bur. Stand. (United States

Government Printing Office, Washington, 1971), No. 35. 

13 W. C. Martin and A. Musgrove, "Ground Levels and Ionization Energies for the Neutral Atoms."

More recent and more accurate ionization energies are given for some elements than the values in

Table 10.3 of Atomic, Molecular, and Optical Physics Handbook, G.W.F. Drake, Ed. (AIP Press,

Woodbury, NY, 1996). 

14 B. G. Wybourne, Spectroscopic Properties of Rare Earths (Interscience, New York, 1965). 

15 Z.-C. Yan and G. W. F. Drake, Phys. Rev. A 50, R1980 (1994). 

16 W. C. Martin, J. Opt. Soc. Am. 70, 784 (1980). 

17 G. W. F. Drake, Adv. At. Mol. Opt. Phys. 32, 93 (1994). 

18 U. Fano and W. C. Martin, in Topics in Modern Physics, A Tribute to E. U. Condon, edited by W.

E. Brittin and H. Odabasi (Colorado Associated University Press, 1971), pp. 147-152. 

19 B. Edlén, Metrologia 2, 71 (1966); E. R. Peck and K. Reeder, J. Opt. Soc. Am. 62, 958 (1972). 

20 T. J. Quinn, Metrologia 30, 523 (1994). 

21 A. G. Maki and J. S. Wells, Wavenumber Calibration Tables from Heterodyne Frequency

Measurements, NIST Spec. Publ. 821 (1991). 

22 C. J. Sansonetti and K.-H. Weber, J. Opt. Soc. Am. B 1, 361 (1984). 

23 B. A. Palmer, R. A. Keller, and R. Engleman, Jr., Los Alamos National Laboratory Report

LA-8251-MS, UC-34a (1980). 

24 B. A. Palmer and R. Engleman, Jr., Los Alamos National Laboratory Report LA-9615, UC-4

(1983). 

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Atomic Spectroscopy: An Introduction
25 S. Gerstenkorn and P. Luc, Atlas du Spectre d'Absorption de la Molécule d'Iode entre 14 800-20

000 cm-1 (Editions du CNRS, Paris, 1978); S. Gerstenkorn and P. Luc, Rev. Phys. Appl. 14, 791

(1979). 

26 V. Kaufman and B. Edlén, J. Phys. Chem. Ref. Data 3, 825 (1974). 

27 G. Norlén, Phys. Scr. 8, 249 (1973). 

28 G. Nave, S. Johansson, R. C. M. Learner, A. P. Thorne, and J. W. Brault, Astrophys. J. Suppl. Ser.

94, 221 (1994), and references therein. 

29 J. E. Sansonetti, J. Reader, C. J. Sansonetti, and N. Acquista, "Atlas of the Spectrum of a

Platinum/Neon Hollow-Cathode Lamp in the Region 1130-4330 Å." J. Res. Natl. Inst. Stds. Tech.

97, 1 (1992), and references therein. 

30 Astrophysical Quantities, edited by A. N. Cox (American Institute of Physics Press, New York,

1996), 4th ed. 

31 A. W. Weiss, J. Quant. Spectrosc. Radiat. Transfer 18, 481 (1977). 

32 H. R. Griem, Spectral Line Broadening by Plasmas (Academic, New York, 1974). 

33 J. R. Roberts and P. A. Voigt, J. Res. Natl. Bur. Stand. 75, 291 (1971). 

34 I. I. Sobelman, Atomic Spectra and Radiative Transitions (Springer, Berlin, 1992), 2nd ed. 

35 A. T. M. Wilbers, G. M. W. Kroesen, C. J. Timmermans, and D. C. Schram, J. Quant. Spectrosc.

Radiat. Transfer 45, 1 (1991). 

36 J. Blaise and J.-F. Wyart, Energy Levels and Atomic Spectra of Actinides, International Tables of

Selected Constants (Tables Internationes de Constantes, Paris, 1992), No. 20. 

37 W. L. Wiese, J. R. Fuhr, and T. M. Deters, J. Phys. Chem. Ref. Data, Monograph 7 (1996). 

38 J. R. Fuhr, G. A. Martin, and W. L. Wiese, J. Phys. Chem. Ref. Data 17, Suppls. 3 and 4 (1988). 

39 W. C. Martin, in Atomic and Molecular Data for Space Astronomy, Lecture Notes in Physics,

edited by P. L. Smith and W. L. Wiese (Springer, Berlin, 1992), No. 407, p. 121. 

Pages designed and maintained by the Office of ECSED. 

Inquiries or comments: www@physics.nist.gov. 

Online: February 1999 

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Atomic Spectroscopy: An Introduction