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TO
ATOMIC SPECTRA
BY
HARVEY ELLIOTT WHITE, PH.D .
Assistant Pr ofessor of Physics, at the
University of Californ ia
fu l arc was first allowed to pass t hrough a sodium flame just in front
of t he slit of a spectroscope, two black lines appeared in exactly t he same
position of the spect ru m as t he two D lines of t he sun's spectrum. Not
many years passed before evidence of t his kind pr oved beyon d doubt
t hat many of the elements found on the earth were to be foun d also
in the sun . Kirchhoff" was not long in coming forward wit h t he t heory
that the sun is sur rounded by layers of gases acting as abso rb ing scree ns
for the brig ht lines emitted from the hot surfaces beneath .
Fr a unhof e r Lines
, I
1Cd'--" --I.
Hydrogen
- -'.J t
0.0 004 0.0005 0.0006 Millimeter s
4000 5000 6000 A ng stroms
FIG. 1.3 .- T he Balmer ser ies of hydrog en .
hydrogen, pointed ou t that the first, second , and fourth line s were t he
twentieth, twenty-seventh, and t hirty-second harmonics of a fundamen tal
vibration who se wave-length in vacuo is 131, 274,14 A. Ten ye ars la te r
Schust er- di scredited this hypothesis by sho wing t hat such a coinc idence
is no more than would be expected by chance .
I STONEY, G. J ., Phil. Ma g., 41, 2!H, 1871.
~ S CH U STER, A., Proc. Roy. Soc. London, 3 1 , 337, 1881.
4 I NTROD UCTIO N TO A TOM IC SP EC T RA [C HAP. I
~ d 5 d 5 d s 0
d L-______ Iil
d ~
D'--- - - I[
K [[D] ~r-------;[IIJL--_
sd sd sd sd 5 d 5 d
I I ! I , !
FIG. 1.4 .- S ch ema ti c representation of t he sodium and potassium series . (After Livein g
and D ewar. )
Angstrom 's
Cal culated wave-len gths D ifferen ce
obse rve d va lues
Whil e t he differen ces bet ween calculated and observe d wav e-lengths
for t he next 10 lines are in some cases as large as 4 A, t he agreement is as
good as could be expected from t he exist ing measurements. The
He<
Balmer Senes
of
HYDROGEN
Stella r a nd Solar Spectra
.lJXK i
. ». . . . .
en!:
- ....-- ---.....
"'~-"'-~~--------";'_
......... ... .._ • ..J x Pegasi
ex Lyr
Solar
~==~~:;:~=,:=:;::=:~~===~========!!
-.::::to o co lJ)
Eclipse
0.. 0 N 0 ~
'0"'......0. N) co...... <:>;:)l; ~
sepa ration of 1574 A, one line lyin g in t he green at >"5350 and t he ot her
in t he nea r ult ra-violet at >"3776. T his discovery proved to be of con-
siderable importance, as it suggested the possibility that a ll series arising
from t he same element were in some simp le way connected wit h each
ot her.
Using Liveing and Dewar's data on the sodium and potassium
series, Rydberg made for the first time the distinctio n between what is
called a sharp seri es and a dt":ffuse series . T he Na and K series given in
Fig. 1.4 were each shown to be in realit y two series, one a series of sharp
doub lets (designated by s) and t he ot her a series of diffuse doublets (des-
ignated by d).
A t hird type of series found in many spectra is the so-called principal
series, involving as its first member the resonance or persistence line of t he
entire spectrum . Resonan ce or persistence lines are t hose relatively
st rong lines most easily excited. Such lines usually appear st rong in a
Bunsen flame. The yellow D lines are a good exam ple of t his.
Still a fourth type of series was discovered by Bergmann. T his type
of series is usually observed in the near infra-red region and' is sometimes
called t he B ergmann series. Since Bergmann did not discover all such
series, H icks called t hem the fundam ental seri es. Although t his name is
per ha ps less app ropriate t ha n t he ot her and is rea lly misleading , it has
afte r 20 years become attached to t he series. New series were dis-
covered so ra pidly abo ut t his t ime t hat ma ny different nam es and
systems of notation arose. Three of t hese systems commonly used are
given in t he following table.
TABLE 1.3.-8ERIE S NOTATION U SED BY D I F F E R E N T INVESTIGATORS
C n = 2, 3, 4, 5, . . .
Vn = V oo - - --, 00 , (1.2)
n + J.I.
where 1'" is t he wave number of t he give n line n , and 1' .. , C, a nd J.I. are
constants. In t his eq uation, 1'" approaches 1' .. as a limi t, as n a pproaches
infinity. While t his formula did not give t he desir ed acc uracy for an
entire series, R ydberg was of t he opinion t hat t he for m of t he eq uation
could no t be far fr om correct.
The nex t eq uation in vesti ga ted by R ydber g was of t he form
N
1'" = 1' .. - (n + J.I. )2' n = 2, 3, 4, 5, . . . 00 , (1.3)
where, as befor e, Nand J.I. are constants, 1' .. is t he limi t of t he series, and
n is t he ordina l number of t he lin e in t he series. This formula proved
o1~1410,00l I I
30.000 cm- 20,000
f
_ .,.,8
' - - Pn
5
--I
-'-
- EI
- :....
R
vn ~ Voo - (n ')1 )2
25 Principol S eries
LIT HIUM
FIG . l. 6.- F r eq u en cy plot of th e principal series of lithium.
If we now let I'~, I'~, I'~, and I'~ represent 1'" for t he shar p, principal,
diffuse, and fundamental series, resp ecti vel y , t he n t he four genera l
series m ay be represented by
Sharp series:
R
(n +
8)2' where n = 2, 3, 4,
• • • 00. (1.5)
8 I NTROD UCTION TO A TOMIC S PEC T RA [CHAP. I
Principal series :
109721.6
v~ = 28601.6 - (n + 0.5951) 2 (1.9)
109721.6
v~ = 43487.7 - (n + 0.9596i (1.10)
28598 5 109721.6
Vn
d
= . - (n + 0.9974 ) 2' (1.11)
=
vd
n (1 +R P )2 (n +R D) 2 (116 )
.
It was not until 1896 t hat Rydberg! discovered, as did Schust er " in
the same year, t hat t he first line of t he principal series in t he alkalies
is also t he first member of t he sha r p series when taken with negati ve sign.
If n is placed equa l to uni ty in E qs . (1.9) and (1.10), t hen vi = -lIl ' In
exactly t his same way it was found t hat t he difference betw een t he limit
of the principal series and t he common limit of t he sha rp and diffuse
series is equal t o t he first memb er of t he principal series :
v~ - 1I ~ = III = -1I 1. (1.17)
These import an t relations are now kn own as t he Rydberg-Schu ster law.
Immediat ely upon t he discovery by Bergmann, 12 year s lat er , of t he
fundamental series, Runge an nounce d t hat t he difference bet ween t he
limits of t he diffuse and fundam ent al series is equa l to t he first line of
the diffuse series :
lIj - li to = 1I~ . (1.18)
Hence, fro m E qs . (1.7) and (1.18), Eq. 1.8 can be written
1 _ R _ R , ()
li n - (2 + D )2 (n + F )2 1.18a
and this equ ati on added to t he group (1.14), (1.15), and (1.16) shows
that the fre qu en cy limit of everyone of t he four series has now been
expressed in te rms of t he constants of some other series. F or t he diffuse
series, n usually starts wit h two in place of uni ty.
The Rydberg-Schu ster law as well as t he R unge law is shown in
Fig. 1.7 by plot tin g t he spectral frequ en cies, in wave nu mb ers v, against
the order number n, for t he four chief series of sodium. T o prevent
confusion amo ng t he lines belonging to t he different series eac h one is
plotted separately. In order to show t hat t he first membe r of t he
principal series becomes t he first member of t he sharp series, whe n taken
with negati ve value, t he scale has been extended to negative wave
number s. Un fortunately t he freq uency scale is to o small to sho w t he
doublet nature of each line. The R ydberg-Schu ster law is indicat ed
by th e intervals Xl of t he figure and t he Runge law by t he int er vals X 2•
A st udy of t he singlet and triplet series discovered in a number of
elements shows t hat similar laws ar e to be found. This may be illus-
1 RYDBERG, J.
R . , Astrophys. J our. , 4, 91, 1896.
2 S CH U STER, A., Nature, 66, 180, 200, 223, 1896.
10 i NTROD UCTIO N TO ATOMiC S P EC T RA [C HAP. I
1 I I Dif fuse
Radiated f requencies 1 1 I Fundamental
SODIUM
CALC IUM
X X4
1--#--4 I: 1 X'I Limit s
FIG. l.8.-Sch ematic p lot of the ch ief triplet an d sin glet series o f calciu m sho wing t h e
Rydber g-S chuster and Runge law s.
v~ = IP - nS, v~, = IP - nD .
v~ = IS - nP, v~ = 2D - nF . (1.19)
In order t o distinguish betwe en singlet-, doublet-, and triplet-series
systems, va rious schemes have been pro posed by different investi gat ors.
Fowler;' for example, used capital let ters S, P , D, et c., for singlets, Greek
lett ers a, 11" , 0, etc ., for doub lets, and small let ters s, p , d, etc ., for triplets.
Paschen and Gotz e" on t he ot her hand ado pted t he scheme of small
letter s s, p, d for both doublets and t riplets, an d capitals S, P , D for
singlet s.
A more recen t scheme of spect ra not ati on , published by Russell, Shen-
stone, and Turner," has been accepted intern ationally by ma ny investi-
gators. In t his new system capital let ters are used for all series and small
superscrip ts in fron t of each let ter give t he multiplicity (see Table 1.4).
T AllLE 1.4.- SERIES NOTATION
Singlet . . . . .. . ... . . . .. . . . . . . . . . . . . . . . . . S P D F S P D F IS Ip ID IF
Doublet .. . . . . ... . .. . . .. . ... .. .. ... . . . . U 7r 0 <P S P d f 2S 2p 2D 2F
Triplet .. . . . . . .. . . ... . .. . . . . . . . . . . . . . . . s p d f s p d f 3S 3p 3D 3F
11
Limits 4th. 3rd. 2nd. lsi.
FIG. 1.9.- Frequen cy plot of t he dou blet fine str uctu re in t he chief series of -caesiu m.
~~~ l LL~~indpal
. :
~-LLlkh,p
I I I I I •
I I I I
III
Limits
---l!L -llL -L
4th 3rd. 2nd.
Gom,Oo'
1st.
F IG. 1.I D.- Frequen cy plot of the t ri p let fin e st ru cture in t he ch ief se ries of ca lciu m .
1.9 and 1.7) t ha t, while t he first principal doublet becomes the first
sha r p doublet when inverted , t he rever se is t rue for t he t riplet series of
calcium . By inverting the first sharp-series member (F ig. 1.10), t he
lines fall in with t he principal series in order of sepa rations and intensities.
SEC. 1.7] E ARLY HISTORICAL DE VEWPMENTS 13
In t he development of Rydberg's formula, each member of a series
was assumed to be a single line. In t he case of a series where each
member is made up of two or more components, t he constants v .. and J.I
of Eq . (1.4) mu st be calculat ed for each component. Rydberg's formulas
for the sharp series of triplets, for example, would be written, in the
accepted notation,
R R
v"n = (1 + 3P - (n + 3S = 13P 2 - n 3S I,
2)2 1)2
R R
13P 1 - n 3S 1,
v"n =
(1 + 3P 1)2 - (n + 3S1)2 = (1.20)
R R 3 3
v"n = (1 + 3P O)2
- (n + 3S1)2 = 1 P o - n S 1,
Internation ally
Series Fow ler Paschen
adopted
later that each letter and number has a definite meaning, in the light of
present-day theories of atomic structure.
1.8. The Lyman, Balmer, Paschen, Brackett, and Pfund Series of
Hydrogen.-It is readily shown that Balmer's formula given by Eq. (1.1)
is obtained directly from Rydberg's more general formula
R R
(1.22)
P
n
-
- (nl + J.Ll) 2 -
(n2 + J.L2)2
by placing J.Ll = 0, J.L2 = 0, nl = 2, and n2 = 3, 4, 5, Inverting
Eq. (1.1),
1 1 1 ni
>.: = a- an~ = Pn ,
. (1.23)
= R (1 1) , where.n2 = 3, 4, 5,
Pn ,2 2 - n~ (1.26)
Paschen series:
Knowing the value of R from the well-known Balmer series the positions
of the lines in the other series are predicted with considerable accuracy.
The first series was discovered by Lyman in the extreme ultra-violet
region of the spectrum. This series has therefore become known as the
Lyman series. The third, fourth, and fifth series have been discovered
SEC . 1.9} EARLY HISTOR ICAL DEVELOPMENTS 15
where t hey were pr edicted in t he infra-red region of the spect rum by
Paschen , Bracket t , and Pfund, res pectively. The first line of these five
series ap pears at Al215, ;\6563, ;\18751, M05 00, and ;\74000 A, respec-
tively. It is to be seen from the formulas that t he fixed terms of the
second, third, four th, and fifth equ a tions are t he first, second, t hird, and
fourth running terms of t he Lyman series . Similarly, t he fixed terms of
the t hird, fourth, and fifth equ ations are t he first, second, and t hird
runni ng terms of t he Balmer ser ies; etc. This is known as the Ritz
combination principle as it applies to hydrogen .
1.9. The Ritz Combination Principle.- P redictions by the Ritz
combination principle of new series in elements other than hydrogen
have been verified in many spectra. If t he sha rp and principal series of
the alkali metals are represented, in t he abbreviated notation , by
Sharp: P" = 12P - n 2S , where n = 2,3,4, ,
(1.30)
Principal : P" = 12S - n 2p , where n = 2,3,4, ,
ihe series predicted by Ritz are obtained by changing the fixed te rms
12P and 12S to 2 2P, 3 2P and 2 2S , 3 2S , et c. The resultant formulas are
of the following form:
Combina tion sharp series:
22P - n 2S , where n = 3, 4, 5,
(1.31)
3 2P - n 2S , where n = 4, 5, 6,
etc .
Comb ination principal series :
2 2S - n 2p , where n = 3, 4, 5,
(1.32)
3 2S - n 2p , where n = 4, 5, 6,
etc.
In a similar fashion new diffuse and fundamental series are predicted
by cha nging the fixed 2p term of the diffu se series and the fixed 2D term
of the fundamental series.
Since all fixed terms occurring in Eqs. (1.31) and (1.32) are included
in the running terms of Eqs. (1.30), t he pr edicted series are simply com-
binations, or differences, between terms of t he chief series. Such series
have t herefore been called combination series. Ex tensive investigations
of the infra-red spectrum of many elements, by Paschen, have led to t he
identificati on of many of the combination lines and series.
In t he spectra of the alkaline earth element s t here are not only the
four chief series of triplets 3S , 3p , 3D, and 3F but also four chief series of
singlets lS, lp, lD, and IF. Series and lines have been found not only
for triplet-triplet and singlet-singlet combinations but also triplet-singlet
and singlet-triplet combinations . These latter are called intercombination
lines or series.
16 INTRODUCTION TO ATOMIC SPECTRA [CHAP. I
Vn = R(~
p2 - 1),
q2 (1.33)
and realizing that p and q must be funct ions involv ing the order number
n, Ritz obtained, from t heoretical considerations, p and q in the form of
infinite series:
(1.34)
Using only the first two terms of p and q, Ritz's equation becomes
identical with Rydberg's general form ula which is now to be considered
only a close approximation. In some cases, the first three terms of the
expansion for p and q are sufficient to represent a series of spectrum lines
to within the limits of experimental error.
1.11. The Hicks Formula.- T he admirable work of Hicks! in develop-
ing an accurate formula to represent spectral series is worthy of mention
at this point. Like Ritz, Hicks starts with the assumption that Ryd-
berg's form ula is fundamental in that it not only represents each series
separately but also gives the relations exist ing between t he different
series. Quite independent of Ritz, Hicks expanded the denominator of
Rydberg's Eq. (1.3) into a series of,terms
abc
n + p. + n + n2 + n3 + (1.35)
H 1 0 0
He 4 0 .0111 0 .0047
Li 7 0.047 0 .026
Na 23 0 .144 0.113
K 39 0 .287 0 .221
Rb 85 0 .345 0.266
Os 133 0.412 0.333
I BIRGE. R . T oo A str ophy• . J our.• 32, 112 . 1910.
TABLE 1.7.-THE RITZ FORMUL A ApPLIED TO THE SODIUM SERIES OBSERVED BY WOO D
(Calculations aft er Birge) 1
R
v" = A - (
n +a +n
b)2'
2
where A = 41,450.083 cm r ", R = 109,678.6 cm" ', a = 0.144335, and b = -0. 1130286 ·
Calc. Cal c. Ca lc .
n Av a c obs . n Av a c obs. n Av a c obs .
diff . diff. di ff.
-
2 5897 .563 0.00 18 2432 .08 -0 .0 1 34 2418 .03 +0 . 01
3 3303 .895 0 .00 19 30 .07 -0 .02 35 17 . 75 +0 .02
4 2853 .63 -0 .04 20 28 .3 7 -0 .01 36 17 .4 5 0 .00
5 2681.17 + 0 .09 21 26 .93 + 0 .02 37 17 . 21 + 0 .03
6 2594 . 67 +0 .09 22 25.65 +0 . 03 38 16 .9 8 + 0 . 04
7 2544.49 -0 .05 23 24 .53 + 0 . 01 39 16.76 + 0 . 03
8 2512 .90 + 0. 07 24 23 .55 0 .00 40 16.54 +0 . 02
9 249 1 .36 - 0 .0 4 25 22 .6 9 0 .00 41 16 .35 + 0 .03
10 76 .26 +0 .03 26 21.93 +0 .02 42 16 . 17 + 0 .02
11 65 .1 8 +0 .10 27 21 .25 + 0 .01 43 16.02 + 0 .03
12 56 .67 + 0. 05 28 20 .6 7 +0. 04 44 15 .86 .. + 0 .04
13 50 .11 + 0 .04 29 20 .15 +0.07 45 15.71 + 0. 03
14 44 .89 -0 .03 30 19 .65 + 0. 06 46 15 .59 + 0. 05
15 40 .71 + 0 .01 31 19 . 09 - 0 .05 47 15 .43 + 0. 01
16 37 .35 +0.06 32 18 .74 0 .00 48 15 .29 - 0. 01
17 34 .50 +0.04 33 18 .36 - 0 .01 49 15 .15 - 0 .04
1 BIRG E, R. T. A s/roph y s. J our ., 32 , 11 2,1 910.
1.13. Neon with 130 Series.- T he first successful ana lysis of a really
complex spe ctrum was made by P aschen I in t he case of neon . Althou gh
the neon spectrum was foun d to contain a great many lines, P aschen was
able to arrange them into 130 different ser ies. T hese series, classified
as 30 principal series, 30 sharp series, and 70 diffuse ser ies, were found to
be combi nations between 4 series of S te rms, 81, 82, 83 , and 84 ; 10 ser ies of
P terms, PI, P2, Pa, . . . ,PI0; and 12 series of D te rms, di, d 2 , d a, •.. ,
d 12 • P aschen showed t hat, while ma ny of t he series were regular and
followed a R itz formula, others were irr egular and could not be fit ted to
any form ula. T hese ab normal ser ies will be discussed in t he following
section.
1.14. Normal and Abnormal Series.- Occasionally it is found t hat
certain members of a well-established serie s do not follow t he ordinary
Rydberg or R itz formula to within t he limits of experime ntal error.
Well-known series of t his kind were point ed out by Saunde rs in the
singlet series of Ca, Sr, and Ba, an d by P aschen in certain neon series.
A convenient method, employe d by P aschen and ot hers, for illustrating
deviations from a normal series is to plot f.L , t he residual constant in t he
Rydberg denomi nator, of each te rm aga inst n, t he order number of the
1 P ASCHE N. F. , Ann. d. Phys., 60, 405, 1919; 63, 201, 1920.
S E C. 1.14] E ARLY HISTORICAL DEVELOP11JEN T S 19
term. Several of the diffuse series of terms of neon as given by Paschen
are reproduced in Fig. 1.12. A normal ser ies should show re siduals t hat
follow a smooth curve like the first nine members of the d 4 series. The
curves for the d 1 , d 3, and d 5 terms sho w no such smoot hness, m aking it
very difficult to represent t he series by a ny t y pe of series formula .
A series following a Rydberg formula is represented on suc h a graph
by a horizontal line, i .e., JL constant. With a normal series like d 4 of
0.035
......
0.030 / .-- <,
'% ~
0.025
. /~
ta 020 ~..
;;;.-- ~ <, 1/
/'
-,
.-2/
1°. 015
0010
d ·.s-:" ~
0 005
Neon
0000
3 4 6 7 8 10 II
- n ~
F IG. 1.1 2.- Four di ffu se ser ies in n eon sho wing no rmal and abnormal progression of t he
residual J.L. (Aft er P a schen .)
between the t wo satellit es f and c and the in terval between the satellite
c and the chief line a that follows Hartley's law of equal separations in
both series . In cadmium it is seen that the main lines and satellites
converge toward t he t hree series limits very early in the series. In
calcium, on t he other hand, t he lines first converge in a normal fashion,
t hen spread out anoma lously and conve rge a second time toward t he
three series limits. These irregulari ties now have a ve ry beautiful
explanation which will be given in detail in Chap. XIX.
0 b c d e f a b c d e f
I I , --L-I I I I ,
II lL- 2 I I. 1.1....-
L IL 3 It II,
~ IL 4 I. IL
h 11 e I, IL
I, II, 6 1\
I I I I 7 ~
I I. l
"
I. II, 9
8
1
1 ~ 10 I
1
• 11
The Balmer and Pi ckering series are both shown schematically in Fig.
1.14. So good was the agreement between calculated and observed
wave-lengths that the Pickering series was soon attributed to some new
form of hydrogen found in the stars but not on the earth.
SEC . 1.161 EARLY HISTOUICAL DEVELOPMENTS 21
Since n2 was allowed to take on half -in tegral values, Rydberg predicted
new series of lines by allowing n l to take half-integral values. One series ,
for example, could be written
All of the lines of this predicted series, except t he first , are in t he ultra-
violet region of t he spectrum. With the appearance of a line in the
spectrum of r-Puppis at M688, t he position of the first line of t he pre-
dicted series, Rydberg's assumption was verified and the existence of a
new form of hydrogen was (erroneously) established.
JJill1tJ~ r
Balme-r-Se-r-le-
s------------J
t
JIIJIIIJ
I , , , ,! ! " I
Picker ing Series
, , , , I J ' ,, !, I " " I
[
, , ,
Un = 4R{ 1 _ 1 }, (1.41)
(nl + J.Ll)2 (n2 + J.L2)2
where n2 is integral valued only .
Problem
With the frequ en cies of the four chi ef series of spec trum line s as given for ionized
calcium by Fowl er , "Series in Lin e Spect ra ," construct a diagram similar to the one
shown in Fig. 1.7. Indicate clearl y th e intervals illustrating the Rydberg-Schu ster
and Runge laws.