Darl H.

MeDaniel
University of Cincinnati
Spin Factoring as an Aid in the
Cincinnati, Ohio 45221
Determination of Spectroscopic Terms

The snectroscooic terms arisine from the electron occu-

pancy 2 nonequ&alent orbitals -&I be obtained from an
analvsis of all possible microstates for the configuration in
question but may he obtained more easily from <he product
of all terms arising from the occupation of the equivalent or-
bitals alone (I).' A similar simplification is possible for terms
arising from electron occupancy of equivalent orbitals by
factoring into a and B spin sets. This powerful method was
developed and applied t o atomic spectroscopic terms by
Shudeman in 1937 (3).I t has recently been rediscovered using
a group theoretic approach by Judd (4). Chemists have not
availed themselves of this method due, perhaps, to the limi-
tation of the literature treatments to terms for monatomic
. . of this Daner
soecies. The ournose . . is to aonlv
.. . the method of
spin factoring in a direct, simple fashion to illustrate how the
Runsell-Saunders term svmhols for molecules and for ions in
various crystal fields &ay he obtained. The development
presented will not rely on familiarity with references (3)or
(4).
Spectroscopic Terms for Atoms
As is k n o q , the number of microstates corresponding to
any electronic configuration is given hy the coefficient of the
+
appropriate term in the expansion of (e h)" where the ex-
ponent of e represents the electron occupancy, the exponent
of h represents the hole occupancy, and n is the total number
of electrons that may occupy the set of orbitals. For t h e p or-
+ + +
bitals we have (e h)6 = e6 6e5h 15e4h2 20e3h3 + +
+ +
15e2h4 6eh5 he; i.e only one microstate is possible for a
p6 configuration, six microstates forp5 orp', 15 forp4etc., and
in general n!/n.!nh! microstates for a configuration of n. Figure 1. Some partial terms from semimicrostates
electrons and nh holes distributed among n spin orbitals.
Factoring the polynomial into a and B spin sets we have (e,
+ h,)"/2(es +hs)"I2. For the p orbitals we have
(ee3 + 3ep2kp+ 3ephp2+ hd3)
+ 3eR2k,+ 3enkn2+ hU3)(ep3 partial tern has a well defined M s value, and each product
of partial terms has a well defined M s value. The product of
Partial terms2 mav he associated with the semimicrostates2 the partial terms associated with particular sets of semimi-
of the spin factored polynomial by inspection of the ML values crostates may thus be associated with single columns in the
arisine from a articular orbital occupancy
. . (see Fig. 1). The usual Mr Venus M Qarravs used to obtain suectroscooicterms.
ML v&es for each semimicrostate are simply the sum of the The product of the a and 8 semimicros&tes automatically
ml values of the occupied orbitals and a partial term of a given vields Pauli allowed microstates. and the match between the
L value arises from a set of semimicrostates running from ML Dumber of microstates and the tbtal degeneracy of the terms
= -L through Mr. = +L. In the above example the e3 and h3 produced serves as a check on the mechanics of the procedure.
semimicrostates are clearly associated with S terms while the Thus from the partial terms obtained for t h e p orbitals we are
e2h and eh2semimicrostates are associated witb P terms, as in a position to obtain the spectroscopic terms arising from
mav he shown bv an examination of the Mr values of the the entire manifold of microstates possible for the occupancy
se&iiicrostates Gee Fig. 1). The product of p&ial t e r n from of a set of equivalent p-orbitals.
an a soin set and a B soin set eives terms havine L values which A p6 configuration can arise only from (e,3)(eg3) yielding
run idinteger stepi3 from IL: - Lsl through TL, +
LpI. Each an S X S = S. The M s value is zero since the a and p spin sets
are equally populated and the total degeneracy is 1X 1 = 1,
Presented at the 169th National Meeting of the American Chemical so the onlv s~ectroscodcterm is a 'S.
Society in Philadelphia (1975). A p 5 c~nkguration-canarise only from (e,3)(3e02) and
'
For the systematic examination of microstates to obtain term
-
(3em2)(en3)
- vieldine S X P = P with M,T= f H and a total de-
designations see Reference (2). generacy of6. Theonly term arising f i o m p r i s thus a 2P.
The designation semimicrostates ia used to emphasize that only
electrons of one spin type are permitted in contrast to the usual mi- A p 4 configuration contains the microstates (e,3)(3ea) and
(3e,)(es3) as well as (3em2)(3eP2).The former yield an S X P

crostates where hoth a and 8 soins are allowed. Each horizontal line
in Figure 1 contains one aemimicrostaW. Partial terms arise from
semimirrostntes and are thus nswciated with n single spin set.
"or examole the ~roductofoartial terms haviwL values of 3 and
5 would have.^ values of 2,3,4,5,6,7, and 8.
-
= P term with M s = i1 and adegeneracyof 6. Thesemust be
six of the nine microstates of a 3Pterm. The (3e,2)(3es2)
P X P = S, P, and D with Ms = 0 and a degeneracy of 9. The
P components witb M s = 0 complete the 3Pterm, and the 'S
Volume 54, Number 3, March 1977 1 147
and 'D terms account for the remaining microstates with M s
= 0.
A p3 configuration contains the microstates (e,3)(ha3) and
(ep3)(h,3) which give two of the four microstates of a 4Sterm.
The other two components of the 4Sas well as 2D and 2Pterms
come from P X P = S, P,and D resulting from (3ea2)(3ep)and
(3e,)(3ee2).
The p2, pl, and pO configurations give rise to the same
terms as the D ~ D. ~ and
. p6 configurations due to the symmetry
. svmmetries, are given in Table 2. (It may be noted that the
of e and h terms in the polyno&ial expansion.
Table 1gives the partial terms arising from the occupancy
of a single spin set b; a given numher of electrons, or holes, for
the orbitals through g. The number in italics following each
set of partial terms is the appropriate coefficient from the
ex~ansionof (e, + h,)n/2and represents the number of sem-
imkrostates for the particular electron (or hole) occupancy,
which is equal to the sum of the orbital degeneracy of the
nnrtial
r-- ~ - - terms
~ -
~ ~ ~ -
eiven. The nartial terms were obtained from
arrays of Mr, values for semimicrostates of the type shown in
An fm7 yields an S term; hence azl t13 t23 must yield an AI
term. Since we know that a21 yields an Az, and t 13 yields an
A 1 term, then tz3 must yield an A2 term. In like manner a dm5
configuration yields an S term; hence e2t23must yield an A1
term; since t23 yields an A* term, e2must also yield an A2 term.
Finally, from the hole formalism we know that tz2 ( ~ r ) t (8)
2~
must give a Tp term, and since tz3 gives an Az, tz2must give
a T I term. These results, along with those for several other
partial terms ari& from the two electron occupancy of any
degenerate set of orbitals are given by the antisymmetric di-
rect product of thesymmetry species to which the orbital set
belongs, as required by the Pauli exclusion principle.)
Althoueh
- - - ~ - ~ the
~~ ~ ~.
oartial terms of Table 2 were arrived at bv a
consideration of the spectroscopic states for atoms in various
Table 1. Partial Terms Arising from t h e O c c ~ p a n c yof a Single
Sriin Set [either u or 81

~ i ~ uI.r e occLpancv
(elecflon.
An exampleof the use of spin factoring to simplify the de- or holed 0 1 2 3 4
termination of soectrosco~icterms for an f4 confiwration Orbital S e t
f~llows.4An f 4 c&iguration will include microstates arising S S111 S (1)
from e,4, e,3eg, and e,2es2. All terms of high spin multiplicity P Sill PI31
d 811) D (5) PF(101
will he replicated in those arising from microstates of lower f S(1) F(7) PFH1211 SDF
M s values. G I (35)

t (35e"')(hs7) - S[(S)(IG F D S)] total degeneracy = 70

g S (1) G (9) PFHKl36) PFI21G
HIK M
SDI21FG[21
HII21KLN

(he7)135e#)
t (35e"3)(7ep)
(7e,.)(35ep3)
- MS = *2
3[(F)(IG F D S ) ] total degeneracy = 490
Ms = *l (includes
r h e orbital degeneracy is given i n parenthesis: t h e n u m b e r of par-
tial terms, i n square brackets.
Table 2. .Partla1 Terms Arwng from the Occupancy of o (or 81

(21e,2)(21es2) - quintet states above)

I[(HPF)(HPF)] total degeneracy = 441
Ms = 0 (includes quintet
and triplet states
Orbital Sets on Vartour Field Svrnmetrlesa
Electron
Orbital Occupancy
Partial
Term
Electron
Orbital Occupancy
.-
Partial
Term
--

above) Under 0 and Td Under D ,

The above yields 5(1G F D S), 3[P(3) D(2) F(4) G(3) H(4)
I(2) K(2) L MI, and '[S(2) D(4) F G(4) H ( 2 ) I(3) K L(2)
Nl
Spectroscopic Terms lor Molecular Specles and for Atomic
SDecles In Nonspherlcal Cryslal Fleldss
The spectroscopicterms into which the free atom states are
split by a reduction in symmetry may be determined by the
methods of group theory and are independent of the spin
multiplicity of the states involved (6). Accordingly, we can use
the correlation of free atom states and states in lower sym-
metry to assign the partial terms arising from the occupancy
of a single spin set of orbitals (either a or 8 ) in various sym-
metries. In a cubic field (i.e. under symmetry group 0)an s
orbitalgoestoanal,pgoestotl,dtoe+tp,ftoa2+t~+tz,
etc.; and an S state goes to an A1 state, a P state to a TI state,
etc. From this it follows immediately that a zero population
of an orbital set yields an A1 (or its equivalent) state, and that
an occupancy of an orbital set by one electron yields the same
designation for the term as for the orbital. Since the p orbitals
retain their degeneracy under 0 symmetry, being designated
terms arising from occupancy of the
as t under 0, the
t t orbitals may he obtained directly from those of the p or-
bitals; i.e.
P.,O yields S t 10 yields A t
p,,' yieldsP t l l yields TI
p,: yields P tl2yields TI
p,: yields S t13yields At
Gwup theory has heen used lo develop the terms for the full/"
manifold ( 5 0 ) and thefinmanifold (5bJ.
;Tables of direct ~nrductr.and correlation tables mav be found in
reference (12). The methods bywhichsuch results ma; be obtained
are detailed in group theory texts, such as reference (9).
0
1 1
0 0
1 1
0 0
1 1
2 0
0 1
1 0
2 1
3 2
0 Under D ,
1 0
2 1
3 0
Under D, 1
0 0
1 1
0 0
1 1
0 0
1 1
2 2
0
1
2
Under D- Under I
o 0
1 1
0 0
1 1
0 2
1 3
2 ' 0
0 1
1 2
2 3
0 0
1 1
2 2
3
4
0
1
2
3
4
a In symmetries for Which g a n d u or ' and " are appropriate labels
Odd electron occupancy of u a t " orbitals rerultr in u o r " partial
terms; all others will be labeled g or '.
symmetries, the use of the partial terms for generating spec-
troscopic terms does not have this restriction. A few examples
of applications follow.
The spectroscopic terms for a tz3 configuration in 0 sym-

+ + +
+
metry would be IAg (from tZa3X ha3 ha3 X t q 3 ) 2A2 2E
2T1 2T2(from 3tzm2X 3tzO1 3tza1 X 3hO2 T I X T z ,
note that the A2 arising from this product contains the Ms =
-+ +
f$ needed to complete tbe 4Az already found.)
The spectroscopic terms of an e 2 configuration under D s

+ +
h,2 X ea2) 'A1 ' E (from 2e,' X 2eS1 E X E which
contains the Ms = 0 component of the 3A2 term).
-
Da, Ds etc. or 0 symmetry would be a 3A2(from ee2 X h p 2 +
B%++
5
*ttf * * + %lt+
2
,+-%
A r 2 configuration is quite similar to the e2 configuration T2s 4~1g 3~2,, Es '"r.
+ +
vieldine a 32- ' Z + ' A . In this case the 'A arises from the
-
.. . .. -....-. Figure 3. Some ground state terms in a weak 00field.
There are, of course, other methods for obtaining the results
of the last few examples (7).The primary difficulty lies in the for dZ (ignoring spin pairing energy and configuration inter-
assignment of spin multiplicity to the individual terms. The actions) would be
eas; of makingsuch assignments appears to be the prime d"' < e"'dl < e'2 < ale" <ale' <at'%
virtue of this method.
Using the spin factoring approach one may readily convert The terms for nonequivalent electrons may be ohtained in
one-electron energy level diagrams into qualitative spectro- the normal fashion as the sinelet and triolet s t a w arisine from
scopic term diagrams for any electron population. One-elec- the direct product of the r&resentatibns designated i y the
tron energy level diagrams for the crystal field splitting of orbital labels; i.e.
d-orbitals in most eeometries mav be readilv obtained bv the
(6
n d ~ c h a a p For example, a
methods of ~ r i s h i a m u r t ha ~
trieonal hinvramidal eeometrv (Dl*) -
. -... .
oroduces the followine
s t A g fi& knergy oAer
The doubly occupied alf orbital would give only the 'Al' term.
The terms for which spin factoring offers simplification are
those arising from equivalent electrons-the e'2 and e"2
configurations.Remembering that ' X ' = 'and " X " = ', while
X " = " all of the doubly occupied equivalent orbitals must
from which the order of energies of the electron configurations give terms labeled '. The e2 configuration under D3 has been
worked out above, thus

and
3A2', l A { and lE'

The strong field limit term diagram is illustrated in Figure 2.

The term diagram in the weak field limit may be obtained in
a straiehtforward fashion from the enerw levels of the d2
terms and correlation tables for the ~ 3 a n d ~ J g r o u pWood
s.
has ouhlished a comdete enerw "- level diaeram for d q n D t..,r.
symmetry (10).
Althouehthe number of microstates vieldine a oarticular
term is e&al to the total degeneracy ofthe te;m, it is some-
times useful to consider a sinele microstate obevine Hund's
rules of maximum mukiplicit; as the "ground state-configu-
ration" and to associate with it the ground state spectroscopic
term. This has been done for the d electrons in a crystal field
of Oh symmetry in Figure 3. Since a completely filled a or 13
d-shell gives no contribution to the orbital term, the orbital
desienations for d6 throueh d l 0 are a repetition of those for
dl &rough d , and indeed'the manifold (;fterms of maximum
multiolicitv will he identical. leading to the same spin allowed
trans~ilons.inthe crystal field spectia. The grounditate terms
mav he written by inspection from a knowledne of the p a n ~ a l
terms and remen&ri;lg that the product of AZ and T;or T2
changes the T subscript, but the product of A2 and E is just
E. The hole formalism relates the spectra of states of similar
spin multiplicities in the well-known manner (9).

3->
I

31
2,
Calculations have recently been made on the electronic
structure of a number of boranes (11). For the unknown
BmHlo4- with a pentagonal dodecahedra1 arrangement (point
group l h l it was predicted that the ground state electronic
A2 configuration would he (h,)"(fis. The determination of the
Orbital
full set of spectroscopic terms for all permitted multiplicities
Terms Occupancy of this one confiewation would he a formidable task bv con-
Figure 2. correlation diagram f w me d2 configuration in a %bongOh field. ventional metho&. The terms arising fromg4 and h6 config-
Volume 54, Number 3, March 1977 1 149
 urations are developed helow.6 T h e full manifold of terms Thanks are due Professor John J. Alexander for useful
from h6g4would of course he the direct product under Ih of suggestions regarding this manuscript.
all of the terms fromg4 with all of the terms from h6, a total
of some 1144 terms. Literature Cited
I11 Henber&G.,"Atomi~SpedraandAtomicStrueture."Do~~rPYbli~~ti~n~.NewYork,
Total 19U.l
Degener- I21 Douglan.8. E..and McDaniel, D. H., "ConeepUandModelsofInorganicChemistry."
John Wiley and Sons, Ine.. NewYork. 1966;Hyde, K. E.. J. CHEM. EDUC., 52.87
acy (19751.
I31 Shudeman, C. L. B.,J. ~ m n k l i nInaritute, 224,501 (19371.
I41 Judd, B. R.,Phya. Re"., 162.28 119671.
151 la1 Curl, JI., R. F.,and Kilpstriek. J. E., Amer. J. Phys., 28.357 (1960); lbl Wybournc,
B. G . , J C h ~ mPhys.,
. 45. LlW (19661.
16) Beshe, H.,dnn. Phjsib, 4 135 (1929).
I71 Goscinski. 0.,sndOhrn,Y..lnr. J. QunnlumChem., 2.815 (1968);Fard,D.l.,J. CHEM.
EDUC., 49,336 (1972); Ellis, R L., and J@e:H. H., J. CHEM. EDUC.,48,97 (1971):
Mu1liken.R. S.,Reu. Mod. Phys.. 4, i (19321.
I81 Krishnarnurthy. R.,sndSehaap,W. 8..J.CHEM.EDUC.,46,799 (19691.
I91 Cotton. F. A,, "Chemical ApplicationsofGmupThoory:'2nd Ed.. Wilcy-Intarscience,
Now York, 1971.
1101 Wmd. J.S..lnorg. C h m . 7.852 11968).
1111 Armstmng.D. perkins ins. P.G.,andSt~urart.J.J.P.,J. Chem. Sor., DaltonTrana..

"his example is given solely to illustrate the ~implifirationof a

formidable prohkm hy spin fanoring. The reader should note theeaw
of assignment of spin multiplicities instead of laboring- over theme-
chanics of obtaining direct products.

150 I Jowml of ChemicalEducation