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FEATURE ARTICLE Infrared and Raman Selection Rules for Lattice Vibrations: The Correlation Method

W. G. Fateiey
Chemistry Department, Mellon Institute of Science, Carnegie-Mellon University, Pittsburgh, Pennsylvania 15213

Neil T. McDevitt and Freeman F. Bentley


Air Force Materials Laboratory (LPA), Wright-Patterson Air Force Base, Ohio 45433

(Received 21 December 1970) INDEX .HEADINGS:Selectkm rules for lattice vibrations; Correlation method. INTRODUCTION

With the recent growth in interest in the ir and R a m a n spectra of crystals, it has become very important to know which vibrational modes are optically active. Hornig, ~Winston and Halford, 2 and Bhagavantam and Venkatarayudu a pioneered in developing methods for this. However, heretofore the determination has been a laborious procedure fraught with difficulty and with m a n y points of indecision. Among the latter is the choice of the primitive cell and the correct site s y m m e t r y of each atom. W h a t is needed is a short, straightforward, foolproof method. We propose here an alternate procedure for obtaining the activity of the vibrations from the correlation tables which comes close to meeting these goals. The calculation is reduced to but a few minutes' work. The method will be explained in detail by use of numerous examples. The correlation procedure has been discussed previously in several papers and books dealing with lattice vibrations. 2-5 We have chosen not to review the theory, but to proceed directly to a demonstration of how to use it and the correlation tables to obtain the vibrational selection rules for solids.
I. RULES

assumed structure. I t is far better to know the structure in advance, however. The crystallographic information m a y be obtained from Refs. 7 and 8 or from the original literature. Examples of t h a t which is needed are given in Table I. 6
B. Molecules per Bravais Space Cell

An orderly procedure is outlined below for the stepwise calculation of selection rules predicting ir and R a m a n activity. The reader is warned that in some cases there m a y be slight variations in some of the steps used in this method. However, intelligent reasoning will help him through these cases.

A. Crystal Structure
The crystal structure of the sample must be known. Alternatively one can be assumed, predictions made for the vibrations, and then these predictions can be compared with observations to prove or disprove the
Volume 25, Number 2, 1971

The Bravais space cell is used by molecular spectroscopists to obtain the irreducible representation for the lattice vibrations. The crystallographic unit cell m a y be i d e n t i c a l w i t h the Bravais cell, or it m a y be larger by some simple multiple. This can be ascertained from the capital letter in the x-ray symbol for the crystal structure. For all those crystal structures designated b y a symbol containing P (primitive), the crystallographic unit cell and the Bravais unit cell are identical. (An example from Table I is Pun,, for SrTiOa.) Crystal structure designated with other capital letters (B, C, I, etc.) have crystallographic unit cells which contain two, three, or four Bravais cells. (An example from Table I is I41/ama for TiO>) The irreducible representations obtained from these crystallographic unit cells will contain two, three, or four times as m a n y vibrations as are needed to represent the lattice vibrations of the crystal. This problem of including too m a n y Bravais cells in the crystallographic cell can be eliminated by dividing the n u m b e r of molecules per unit crystallographic cell by a small integer. This integer is identical with the number of lattice points (LP) in a crystallographic cell of specific s y m m e t r y as designated by the capital letter in its symbol. Table I I gives this number, LP, which reduces the size of the crystallographic unit cell to the desired Bravais space cell. This reduction has been included in Table I. In summary, the number of molecules in the Bravais space cell = Z / L P = t h e number of molecules in crystallographic unit cell/number of lattice points Z B (from Table II).
APPLIED SPECTROSCOPY
155

Table I. Cyrstallographic information for several examples.


Crystal structure nomenclature ~ Crystal SrTiO3 TiO2 ( a n a t a s e ) ZrO2 ~-Al~O3 Cu~O NH4I ~ See Refs. 7 and 8. b See Ref. 5. e Phase I I I (see Ref. 6). X-ray Pm3,~ I41/~,.,~ P~/. RS~ P.3,,, P4/ ..... Spectroscopic Oh 1 D4h 19 Cab 5 Dad 6 Oh 4 D4h 7 Molecules per u n i t cell (Z)~
1

Lattice points b (LP)


1

Molecules per Bravais cell ( Z / L P ) - Z ~


1

4 4 '2 '2 2

2 1 1 1 1

2 4 "2 2 '2

C. Site Symmetry of Each Atom in the Bravais Cell


The equilibrium position of each a t o m lies on a site which has its own s y m m e t r y . This site s y m m e t r y is a subgroup of 5he full s y m m e t r y of the Bravais unit cell. I t is v e r y i m p o r t a n t to ascertain the correct site s y m m e t r y for each atom. I t is easy to do this in some cases, difficult in others. Let us consider the following examples.

1. Cu~O
Table I states t h a t the s y m m e t r y is Oh4 and t h a t there are two Cu20 units in a Bravais cell. There are, therefore, four equivalent copper a t o m s and two equivalent oxygen a t o m s in the Bravais unit cell. (This rule is always applicable provided one has found the equivalent a t o m s in a crystallographic cell. This information is provided with the crystallographic structure in Refs. 7 and 8. Appendix I contains this information.) Next, one turns to the table in Appendix I and looks for the e n t r y Oh 4 in the third column. I t is No. 224. I n the right-hand column are t a b u l a t e d all the possible site symmetries for this space group. These are written as T~(2); 2D3d(4); D ~ ( 6 ) ; . . - . T h e y are given in full in T a b l e I I I . These are all the possible kinds of sites for an Oh 4 crystal, but most of t h e m will not be occupied in a specific crystal The most useful information is the n u m b e r contained in parentheses, for it is the n u m b e r of equivalent a t o m s which have t h a t particular site s y m m e t r y . F o r example T~ (2) means t h a t there are two equivalent
Table II. The number (LP) which reduces the crystallographic unit cell to the Bravais space cell.
T y p e of c r y s t a l structm'e A B

a t o m s occupying sites of s y m m e t r y Ta. Similarly Dan(4) indicates the presence of four equivalent a t o m s on Dad sites. Some of the site s y m m e t r i e s have numerical coefficients, such as 2D3j (4) in T a b l e I I I . The coefficient 2 means t h a t there are two different and distinct kinds of D3~ sites in this unit cell. E a c h kind can accomm o d a t e four equivalent atoms. I n a given crystal there m a y be a t o m s on one or both of these sites, or on neither. The second and third columns of T a b l e I I I illustrate the a b o v e remarks. For Cu20 the x-ray results show t h a t there are four equivalent copper a t o m s and two equivalent oxygen atoms. W h a t will be their site s y m m e t r i e s ? F r o m Table I I I (or from the equivalent e n t r y in Appendix I) one s e e s t h a t there is only one site s y m m e t r y which can a c c o m m o d a t e four equivalent a t o m s : D:~,~. Therefore, the site s y m m e t r y for copper is D:~j. Similarly only one kind of site can a c c o m m o d a t e just two equivalent a t o m s : T~. This therefore is the site s y m m e t r y for oxygen. I n selecting the site s y m m e t r y , one m u s t always have the n u m b e r of equivalent a t o m s equal to the a c c o m m o d a t i o n a l value of the site s y m m e t r y . The a b o v e example was atypically simple in t h a t there was no a m b i g u i t y in the result. We t u r n now to another example which is slightly more difficult.

2. TiO=, (Anatase Form)


T a b l e I tells us t h a t the space group is deuignated D4h '9 o r I q / a m d , with two molecules per Bravais unit cell. There are therefore two equivalent t i t a n i u m a t o m s and four equivalent oxygen a t o m s in this Bravais cell. F r o m Appendix I we find t h a t this is No. 141 and has the site s y m m e t r i e s 2D2d(2); 2C2,,(4): C.a,(4); 2C2(8) ; C.,(8), C1(16). Consider first the two equivalent titanium at, oms. Only the D2~ sites a c c o m m o d a t e two a t o m s ; therefore, it follows directly t h a t the t i t a n i u m a t o m s are on sites of D2d s y m m e t r y . T h e r e are two separate kinds of such sites (coefficient 2), but it not necessary for us to know which kind is occupied. For the four equivalent oxygen a t o m s there are two possible site s y m m e t r i e s : C2h and C2~. B o t h w i l l

No. ( L P ) 2 2

c F I P
R

2 4 2 1
3 or 1~

Here the crystallographic group may have a l r e a d y b e e n decreased by three; if so, o n e n e e d n o t divide the crystallographic cell. Simple indication of whether o n e should divide by t h r e e or n o t is found in the example of ~-Al~O3 (Table I) which contains two molecules per unit cell. Certainly, one would not divide by three in this case.

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Volume 25, Number 2, 1971

Table III. Site symmetries for the space group designated O~, 4 or P.~ or 224. (Cu~O).

Table IV. Site symmetry of each atom in various examples.

site symmetry

Bravais cell Td (2) 2D3d (4) D2a(6) C3, (8) D,(12) Csv (12) 3C2(24) C,(24) C1(48)

No. of equivalent atoms on this site of Bravais cell (No. in parentheses) 2 4 6 8 12 12 24 24 48

No. of kinds of sites of this symmetry (coefficient) 1 2 1 1 1 1 3 1 1

Ti02, Example Anatase SrTiO:~, Cu~O A1203, ZrO2, NHd Site of Ti-D2d S~0h Cu-D.~a A1-C3 Zr-C1 NH4-D2a equivalent O-C~ Ti-Oh O-T,i O - C 2 O-C1 I-C4~ atoms O-D4h axes. The simplified description of the vibrational mode allows easy classification into one of the species of the site s y m m e t r y , D2~. F o r example, the displacements of the t i t a n i u m a t o m s parallel to the z axis will have the s a m e character as the translation in the z direction. T h e translation Tz belongs to the species B2 of the site group. Therefore the a t o m displacements parallel to the z axis will also belong to the B2 species. Similarly, the displacements of t i t a n i u m atoms along the x axis will have the same character as T , and belong to species E. I t is i m p o r t a n t to note here t h a t this approach, which classifies the lattice vibration as excursions in x, y, and z directions, is no different from the descriptions used for molecular vibrations such as bond stretching, bendings, and twistings. Of course the normal vibrations in a crystal or a molecule are far more complex t h a n this simple picture provides; however, the i m p o r t a n c e of this m e t h o d is found in the simplicity with which the lattice vibrations can be classified. W h e n the species of the site group is identified for each lattice vibration, t h e n this information is integrated via the correlation tables to the species of the crystal which contain this lattice vibration. To begin this correlation procedure, T a b l e V gives a portion of the D2~ site group and identifies the species of the translations T~, T~, and T , (See Ref. 9 for character tables.) Since the lattice vibrations have the same character as the translations, the species which contain these vibrations can readily be identified and this information is presented in T a b l e V. Before applying the correlations of site to factor group, it is convenient to define some useful t e r m to aid in this integration. (1) t ~= The n u m b e r of translations in a site species ~. This n u m b e r can take the values of zero, one, two, or three depending on whether none, one, two, or three translations are contained in the site species % respectively. This information is readily available from the character table (see Ref. 9).
Table V. Species of the site group D~ and the translations.

a c c o m m o d a t e four equivalent atoms. One or the other will be correct, but additional information is needed to m a k e the choice. For this one turns again to the crystallographic tables, 7,s which state t h a t the oxygen a t o m s lie on C2~ sites. (See Appendix I I for an explanation of how to use the crystallographic tables.) This additional information is needed whenever one meets an a m b i g u i t y of the above type. Table I V gives the site s y m m e t r y of each a t o m in the various examples used in this paper.
D. C o r r e l a t i o n of t h e Site G r o u p to t h e F a c t o r

Group

Different authors v a r y in their choice of the t e r m factor group, crystal group, or correlation group to describe the crystal s y m m e t r y . All those t e r m s are equivalent. Previously the site s y m m e t r y has been found for each a t o m in the lattice and these results are summarized in Table IV. N o w the s y m m e t r y species will be identified for each equivalent set of a t o m ' s displacements in tim site. These displacements we describe will become the lattice vibrations in the crystal. Knowing the site species for these displacements, the correlation tables relate each species of site groups to a species of the factor group. This correlation explicitly identifies the species of the lattice vibration in the crystal and further allows prediction of ir or R a m a n activity. Using the following molecules as examples, first the lattice modes will be identified in the crystal by obtaining the irreducible representation which contains the n u m b e r and species of the lattice vibrations and, second, the ir and R a m a n activity of each vibration will be described.

1. TiO~ Crystal
As s u m m a r i z e d in Table IV, the two t i t a n i u m a t o m s are in D2d sites and the four oxygen a t o m s are in C2~ sites. In this example, each set of equivalent a t o m s will be treated separately. T i t a n i u m Atoms. First, the vibrational displacements of these t i t a n i u m a t o m s in the lattice can be described as simple motions parallel to tbe x, y, or z

D~d Site of Ti atom, species


Ai

Translation species

Ti Atoms excursions

A~ B1 B2 E

T, T,. u

Motions parallel Io z axis Motions parallel to x and y axes


APPLIED SPECTROSCOPY

157

R ~ = T h e number of rotations included in the site species ~. Again this value will be either zero, one, two, or three. The character tables in Ref. 9 clearly identify the rotations as Rx, R~, and R,. (2) i f = The degrees of vibrational freedom present in each site species 7. This can be calculated as follows, where n = n u m b e r of atoms (ions or molecules) in an equivalent set
t'. n = f'. (1)

Here, a coefficient of 2 is added to the E species which must be doubled because of the separable degeneracy. (5) Convenient checks. I t is helpful to check the bookkeeping as the correlation m e t h o d progresses. The following equations, when applied, will help avoid errors. 3n = (degree of freedom)site = ~ f~
,y

(3) (4) (5)

3n = (degree of freedom)~aetor grouv= ~ a~C~, where a~ = ~ a~.

f R ~ = T h e degrees of rotational freedom present in each species y. This can be calculated b y modifying Eq. (1) to give
. f ~ = R ~. n. (la)

(3) a~ will represent the degrees of freedom contributed by each site species ~ to a factor group species ~'. The value of a~ can be calculated as follows: ff = are
r

~Cr.

(2)

(6) The irreducible representation of the crystal gives the number of lattice vibration in each species of the factor group. The total irreducible representation of the crystal, F crystal, is the combined irreducible representation of each equivalent set of atoms, FEq" set" The F~q. set is constructed in the following manner:
r E q . set ~ a ~ - ~, (6)

The derivation of this equation will not be presented here; however, as one understands and uses this method, the origin of this equation will be obvious. The values of Cr are given below. (4) Cr is the degeneracy of the species f of the factor group. An additional superscript, % m a y sometimes be added to show its correlation to a species of the site group. Usual values of Cr are summarized below.
Species
A B E F G H

where at, as previously defined, is the number of lattice vibrations of the equivalent set of atoms in species ~- of the factor group. The total irreducible representation of the crystal r crystal c a n be constructed as follows :
r c r y s t a l __ ~ - - Eq. set 1 - [ - r E q . set 2 - ~ " " " (7)

Value of Cr
1 1 2 3 4~ 5

This irreducible representation of r Cry~tal contains the acoustical vibration. In the following examples, the acoustical vibration will be removed from this representation by simple substracting out the irreducible representation of the acoustical vibrations, as follows : Fcrystal __ p c r y s t a l p a e o u s t i c a l (8)
vibration - - x -- ~

Usually the species designation has either a superscript, e.g., A', A", etc., or a subscript, e.g., A~g, E, F ~ , etc.; however these super- and subscripts in no way describe the degeneracy of the species and for this reason are not included herein. There are exceptions to the above description of degeneracy for certain correlations where separable degeneracy exists. Without a proof, the following modification of the existing correlation tables will give the correct correlation and a~ values. (1) Point group C6, C4h, C6h, $6, T, and Th do not use the 2 coefficient which appears in these correlation tables for the doubly degenerate, E~, species. (2) For a portion of the T and T~, point group correlation tables, modify as follows. T C3 Th $6 C~

is the irreducible representation of the lattice vibrations in the crystal. This procedure needs only minor modification to include the intramolecular vibration and libration for molecular crystals. Here the irreducible representation of a molecular crystal can be defined as
r m o l e c u l a r crystal ~crystal ! vibration = v i b r a t i o n -I- ~ m o l e c u l a r vibration -'1- I~libration - - r acustical-

NOW

-perystal vibration

(9)

F
158

A+2E

Fg Ao+2Eg F~ A,~+ 2Eu

A+2E A + 2E

The molecular crystal NH4I, example 6, will demonstrate the usefulness of Eq. (9). Utilizing the above definition, the degrees of vibrational freedoms for each species of the site group D2a are tabulated in Table VI for the equivalent set of titanium atoms. Table VI indicates the presence of the titanium lattice vibration designated as degrees of freedom in species B2 and E. The next step is to correlate the B2 and E species of the site group D~d to the D4h factor group species. The correlation tables are given in

Volume 25, Number 2, 1971

Table VI. Titanium atoms on site D~a. The degrees of vibrational freedom for each species (n = 2 atoms/equivalent set).

Table Vlla. Correlation for the lattice vibrations of the titanium atoms in TiO~ crystal between the site group D2~ and factor group

D~a species A1 A~ B, Bz E

Translation

T: T:. T,~

U 0 0 0 1 2

Degree of vibrational freedom


.fv = n . U

D4h.

0 0 0 2 4

fv 2

(TD

Correlation D4h Factor a~ D~ Site ) group species, T C~' ~ CV' species, ~" C ar=aB,+aE B2 - ~ ~ B,~ 1 1 1 0
A2. 1 1 1 0

Appendix IV for D2d to D4t,, and also presented in Refs. 9 and 10. E x t r a c t i n g only a portion of the correlation tables given in Appendix IV, we find the following relationship between the site and factor group species. D2d Site group spee.ies
A~ ~

E~

a t o m can be written as the following irreducible representation I~Ti, FTi=I"Blo+i"A2~+I"Eg+i"E~. A check can be m a d e at this point for possible errors utilizing Eqs. (3) and (4), degrees of vibrational freedom in site groups =3n=6=~
Y

Correlation > C:' ~ C:"

,'

D 4h Facior .group species


: Aj U

B~,,

f~=6

A~

.~

A~

degrees of vibrational freedom in factor groups 3n=~


a~C~.= 1 + 1 + 2 + 2 = 6

B~

A,,,
B2o

where n = 2.
Oxygen Atoms. Following this s a m e procedure, outlined above, the irreducible representation, tony, can be obtained for the equivalent set of oxygen atoms. A s u m m a r y of the necessary information is t a b u l a t e d in T a b l e V I I b .

B~

---.-.-...._

B~
A 2,,

Eg
E~

Checks Therefore, there is no need for reproducing a complete set of tables here. Appendix I V treats only two such tables primarily to show how t h e y are derived a n d provide the proper basis for selection of the eorrec correlation tables when two or more possibilities exist. Since only the site species B2 and E contain these translations which are the lattice vibrations in the crystal, the correlations relating these species to those species in this factor group are of i m m e d i a t e interest. B y integrating the site species which contains the translations into the factor group b y the correlation tables, it is easy to identify these lattice vibrations in the factor group species. Table V I I a shows this correlation and identifies the species of the lattice vibration in the crystal. The t i t a n i u m a t o m ' s irreducible representation for the factor group is obtainable through Eq. (4) r=~2 ar'L ~ where a r = ~
T

Eq. ( 3 ) : ~

f'=3n=12

Eq. (4) : ~ a~C~ = 3n = 12[ degrees of freedom. ~J


Table Vllb. Tabulations of terms and correlations necessary to calculate the lattice vibrations of the oxygen atom in Ti02 crystal.

Correlation D4h Factor a~ ) group .f~ H species ~ (C~.~d species ~ Cr ar =aA~+alh+aB2


C~, Site
(T~)Ai 4 1 ID A l g 1 1 1 = 1 -I- 0 + 0

~ ~

. ~

A2g

0= 0+0+0 1= 1 + 0 + 0 o= o + O+ 0 2= 0 + l + 1 0= 0 + 0 + 0 1 = 1 + 0+ 0 O= 0 + 0 + 0
1 = 1 + 0 + 0

- - Bi, B2~

1 1 2

4 1 (T=)B| ~- -- ~ E o ~\ ; " \f/~


\ / \ ~

A,,
A,,

1 1 1
1

[ ~kE,

a~,, i.e., the

n u m b e r of vibrations in

(Tu)B2

species ~'. Therefore, the species of the factor group which contains lattice vibration involving the t i t a n i u m

2= 0 + 1+ 1

APPLIED SPECTROSCOPY

159

Table VIII. D~ factor group, translation, and acoustical modes.

D4~ Species A~

Translation species T~

Acoustical mode species 4

from the irreducible representation as suggested in Eq. 8


l~erystal __ r e r y s t a l vibration - raeoustieal.

The number and species of oxygen lattice vibration can now be calculated, for Foxy= ~ a:. ~',
P o n y = ~ a t . ~"= 1Ai~-4-OA2~-I-iBz~WOB2g+2Eo

+OAi,~-f-iA2u+OBz~+iB2~-4-2Eu

(10)

collecting terms :

Fo~y=A lg + Bi~-4-2Eo+ A 2~-kB2~+ 2E~.


The total representation of the crystal, F crystal, c a n be calculated using Eq. (7) where F crystal is the sum of the individual irreducible representation for each set of equivalent atoms, or
r e r y s t a l -~ 1 ~ Ti " ~ I~oxy FWiO, c r y s t a l =

The acoustical modes are readily identifiable in factor groups since they have the same character as the translation; Table VIII shows this identification. Therefore, the irreducible representation of the acoustical vibration r acustieal = A 2~A-Eu. The results of this factor group analysis identifying the number of lattice vibrations in each species and the spectral activity are summarized in Table IX. Table IX gives the following selection rules for first-order Raman and ir activity in the TiO2 crystal. Raman spectrum: Six fundamental lattice vibrations are allowed A ~ , + 2 B ~ + 3 E , . Infrared spectrum: Three fundamental lattice vibrations are allowed

A2~+2Eu.
One vibration will be inactive in both the ir and the Raman spectrum: B2~. Also, there will be no coincidences, i.e., the same vibration mode which is active and observable by both the Raman effect and in the ir spectrum. This completes the original goal set forth to obtain (1) the number of lattice vibration in TiO2 (anatase) and (2) the spectral activity of these vibrations. Additional information may be obtained by studying the polarization direction of Raman scattering; however, this procedure will not be discussed here.

( B zg + A 2,~-4-E g+ E ~,)+ ( A lg + B zo + 2 E ~

+A~,+B2~+2Eu) =A~+2A2~+2Bz~+B2~+3Et,+3Eu.
Applying a check at this point on ~he vibrational degree of freedom, Eq. (4) gives 3n = ~ at. Cr where n is the number of atoms in the Bravais cell, for TiO~ n = 6 . Therefore 3 . n = 18= 1CA,o+2C~+2C~1~ +iCBz,+3C~,A-3C~. The acoustical vibrations are included in the irreducible representation, F TiO~crystal, given above. Of the 3n degrees of vibrational freedom, three are acoustical modes. When one considers only those vibrations at the center of the Brillouin zone, i.e., k ~ 0 , the three acoustical vibrations have nearly zero frequency. Since vibrations with zero frequency are of no physical interest here, they can be substracted

2. SrTiO3 Crystal
Now that the stepwise procedure has been applied to obtain the molecular vibrations and activity for Ti02 crystal; there are several short cuts which, when applied, reduce the calculation to but a few minntes. SrTi03 crystal will serve as an example of this simplified procedure.

Table IX. D4h factor group species, translations, acoustical modes, number of lattice vibrations, and ir and Raman activity of TiO2 crystal.

D4h Factor group species A;a


A~g

Translation species

Acous~bical rTiO, crystal mode species coefficients 1 2 3

FF~O* coefficients~ 1 2 3 1
1

ir activity b

Raman polarization tensor species

Raman activity

B~ B~ Eg
Ai~

(~ -~)
~zy

~zz

CQyz~zx

A~
Bzu

T, T~, ~

1 1

2
1

4 4

B2~

E,,

pTiO2 _pcrystal TiO~ ~acoustical vib -- 1 (Azo --~-2A2u--~2Bzg--~B2u --t-3Eg+3E~) -- (A2~ +E~) =Aig+A2u-4-2B1g--~-B2~,-~-3Eg+2E.. These coefficients are the number of lattice vibrations present in the species. b Only those species which contain the translations are infrared active, i.e., A2u and E . are the only species which h a v e ir active vibration. Those species which contain the polarizability tensor can have Raman activity, i.e., Azg, Big, B2g, and Eo can have Raman active lattice vibrations. This information is readily available from Refs. 9 and 10.

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Volume 25, Number 2, 1971

Pertinent Information.

Copper.

Crystal: SrTiO~, Pm~m--0~ t, Z ' = 1 (see Table I). Equivalent atom site: Sr--O~(n= 1); Ti--O~(n= 1); oxy atoms--D4~(n=3). (see Table IV).
Irreducible representation of each equivalent set of
atoms
:

.f~

C I(T~) 2 (7'~, ~)

D3~ Site symmetry species containing translation


A2,, ~ E,,

Correlation av ) Oh F a c t o r group species C a r = a A 2 + a B .


~ A2,, "" ~ E. Ft,, 1 9 3 3 1 1 '2 1 1 0 l 0
0

l 1 t

Strontium.
O. site symmetry species containing translation
F,.

F2,,

Correlation

fff 3

l~ 3(T.,~,~)

Oa factor group species Cr ar F,,, 3


i

Fcu =A2~+E,~+2Fi,,+F2,,

) f

Oxygen.
7'd Site symmetry species containing translation F2 ~

".Fs~= ~ a r . f = l . F ~
Titanium.

Correlation

.f* 3

t* 3(T~,.,.)

O~ site symmetry species containing translation F~,,

.U
Correlation)

U 3 (T~, ~,.)

Oh F a c t o r group species " Ft.(T~,~:t F~ o

Cr ar 3 :; t 1

Oh f a c t o r
group species F,. Cr ar 3 1

Foxy = Flu-~-F2e r a c o u s t i e a l -~

FTi= I ' F ~ ,
Oxygen.

Flu.

~Cu~O Irreducible representation of the crystal ~ib.

.P
3

l~
[(Tz)

D ~ Site symmel ry species contailfing translation

rcu~o
vib

FCu+ Foxy-- I~aeoustical

Correlation )

Oh F a c t o r group species
F l , , ( T z , v,, )

a7
C r af=aA~+aE,,
:~ 2 = l l

= (A~,WE~W2F~,WF2u)+ (F~u+F2o)- ( ~ ' l u )


Spectral activity : l~aman--F2g ; i n f r a r e d - - F ~ . Therefore, there will be one F2g active fundamental lattice vibration active in the R a m a n effect and two Fh, ir active lattice vibrations.

A2t,
E,, ~"----

2(T~.~,)

"~ F~,,

1= 0

Foxy= ( 2 F ~ + F : , )
F aeustieal = F 1 u

Summary.

4. ~-AI20s Crystal
p S r ~_ F Ti _~_ F o x y _ Faeoustical

FSrTiO: cryst r i b

(F~)T(F~,,)+(2F,~+E:,,)

(1,)

Information : R~c-D~d6,:ZB= 2 (see Table I). Equiva lent atom site : A1--C3 (n = 4) ; oxy--C2 (n = 6) (see Table IV).

The O, character tables, see Ref. 9, identify F l u a s ir active and F2~ as neither ir nor R a m a n active. Therefore, SiTiOs has three ir active fundamental vibrations and no first-order Raman spectrum. Appendix I I I gives identical irreducible representation by a different, more laborious method.

Aluminum.
C3 Site symmetry species containing translation A '
D.~,t Correlation F a c t o r group species C

a~
a=aA+aE

.f"

l~

I(T:)

A,~ A2u

1 1
'2

1 = 1-{-0 1 = 1 +0
2 = ~l + 2

3. Cu._,O Crystal
h f f o r m a t i o n : OP--P.~m, Z B = 2 (see Table I). Equivalent atom site: Cu-D3h ( n = 4 ) ; o x y - T d (n = 2) (see Table IV). Irreducible representation of each equivalent set of atoms. 2(7'..,)
E

E,j

\\
\

~ ,

A~,,
~A2~

1
1

t = I +0
1 = 1 +0

~" E,,

"2 = (; + '2

APPLIED SPECTROSCOPY

161

Here one observes that aa and a~ have different values. Reviewing Eq. 3, f f = a ~ ~Cr, gives the values of a~. The a~'s are evaluated in the following manner. Site species A : fA=4=aA(CAi-I-CA~+CA~+Ca2~)
= aA

Oxygen
C~ Site symmetry species containing translation A

Correlation

C2h Factor
group symmetry Aa Bg Cr ar 1 1 6 6

f~

t~

( 4 ) .'. a a = 1.

24

3(T~,u,~)

Site species E : f ~ = 8 = a~ (C~, + C ~ ) = a'~ ( 2 + 2 ) .'. a~ =2. T h e n FA~=A~+A~a+A~u+A~u+2Eo+2E~.

Au(%)
B~(T~,u)

1
1

6
6

Oxygen.
C~ Site symmetry species containing translation A

Foxy=6Ag+6Bg+6Au-k6Bu r ..... t i c a l = A u+ 2B ~.
Dsa
Correlation ) Factor a~

Summarizing,
r Zrri0 b2 __ 9Aa(a)+9Bz(It)+8A~(i~) + 7Bu(i~). -

f~

t~

group species ~ A~a

C~ , a~=aATaB
1 1 1 2 1 0 0 2

6 i(T~)

A~

6a. NH4I Crystal (phase III)


Durig and co-workers have made extensive investigations of the molecular crystal, NH4I. 6 This crystal not only possesses lattice vibrations but also libration and intramolecular vibrations of the NH4 group in the crystal. It is worthwhile to repeat Durig's calculations with some modifications to demonstrate the usefulness of the correlation m e t h o d when applied to a molecular crystal. A natural division in applying the correlation m e t h o d to a molecular correlation can be made as follows. (1) Derive the lattice vibration of the NIt4 + ions and iodine atoms. (2) Calculate the libration, i.e., rotation, of the NH4 + group in the crystal. (3) Use the correlation technique to predict the n u m b e r of intramolecular vibration of the NH4 + group. T h e lattice vibrations ~re sometimes referred to as external vibrations while the molecular vibrations within a crystal are called internal vibrations. B y combining the irreducible representation obtained from parts 1-3 using Eq. (9), the total representation for NH4I is constructed.

~'~
12 2 (T~. v)

"U~ Ea A~. A2~(T,) "~" ""~E~,(T~,u)

2 1 1 2

3 1 2 3

1 1 0 1

2 0 2 2

Fo~y=Aao+2A~o+3Eo+A~,+2A~,+3E., and
F . . . . . tial = A 2 . + E ~ ,

Summarizing, Eqs. (7) and (8) give FAI~O, _ rib - (Ala+A2o+Ai.+A2,+2EgT2E,)

(Alo+2A2g+3Eg+Alu+2A2~+3Eu -(A2~+E~)
FAI~O,_ rib - - 2A lgR)+ 3A 2alo ) + 2A I~ R)+ 2A 2u(o )
-~ 5Eo(ir) + 4 E u (jr)

Here one can indicate the activity of each species b y a superscript as follows: ( R ) = R a m a n active; (ir) = infrared active; (0) = inactive. This information is available from the character tables given in Refs. 9 and 10. 5. ZrO2

6b. Lattice Vibrations of N H J Ion and Iodine Atom NH4 + ion. Information: NH4 +, site D2a, Z B= 2 (see Table IV).
NH4 + D2a Site symmetry species containing translation E - ~
"'"-~

Information: P2,/o--Csh 5, ZB=4 " (See Table I). Equivalent atom site : Z r - - C i (n = 4) ; Oxy--C1 (n = 8) (see Table III). Zirconium.
C~ Site symmetry species containing translation

f~

12

3(T~.,,.,)

A. A.
Ba A. B.

Correlation C2h Factor group symmetry

Correlation ) C~'~ C:' ~

Cr a~

f~

t*
2 (Tx, Tu)

Factor group species Cr E~


Eu

044

a~

a~=aEWaB~
1
1
1

t 1 1 1

3 3 3 3

2
2
1

1
1
0

0
0
1

I(T,)

B2 ~'~'~'~

~ B2a A2u

FZr=3Ab+3Bo+3A,,+3B,,
162
Volume 25, Number 2, 1971

~ C=' H, ' :B2a(R)+A2u(i')+Eo FNC

(R)+Ea(ir)

T h e a b o v e correlation applies t h e tables derived in A p p e n d i x V. R e p e a t i n g a p o r t i o n of this table, one realizes there are t w o possible correlations of D:e into D4h. These are given below in T a b l e X a . C o r r e l a t i o n (1) C~' ~ C~' in T a b l e X a was used in the a b o v e calculation, b u t w h a t would be t h e results if correlation (2) C : ' --~ C ~ " is u s e d ? R e p e a t i n g this calculation b u t using t h e second correlation given in T a b l e X which m a p s D ~ d c,' ~ c,'~ D 4 ~ .
NH4 +

Table Xa. Two possible correlations which map D2d into D~.

Factor group
D4~ A2~ B2a

(1)
Cs ~ ~ C~ t

(2)
C2' ~ C~"

D~ B~ Bs

Did B~ Bl

Eo E,
Big

E E
Bx

E E
B2

f~ t~ 4 2(T,,~)

D~ Site symmetry Correlation D4h species ~ Factor a~ containing C~' ~C2" group translation species C i- a~ aE.+-as~ E. ~ .~ Eg " " ' " " ~ E, 2 2
,
~.

Table Xb. NH4 lattice vibrations. The result using two different correlations from Table Xa. The polarizability tensors are given for certain species of D4~ point groups.

Correlation C2' --~ C~'


..

Correlation C2" -~ C~'


Bag

Polarizability tensor~
(,~-o~uv)
~xv

1 1
1 1

1 1
0 0

0 0
1 1

B2g
A2~
Ea E.
a S e e R e f . 9.

A2~
Ea E,

-auz,azx

2 ~ (%)

B 2 ~ > B , ~

T h e results are Correlation (2) J.. ~c~'-~ N H 4 + c~" = Blo(R)--[-A 2u (jr) +Eo(R)+E~(i~), c o m p a r i n g to t h e first calculation Correlation (1) r ~ : ~ c~'=B2 (R)+A2 (i~) + E g ( ~ ) +E~,(i~). B o t h irreducible r e p r e s e n t a t i o n s predict two ir a n d two R a m a n active f u n d a m e n t a l vibrations. I n this specific instance, an i m p r o p e r choice of t h e correlat i o n table does n o t alter the predicted spectral activity. This is n o t the general rule as the reader will find t h r o u g h experience. ( F o r example, see Ref. 11).

W h e n t h e results are c o m p a r e d using b o t h correlations in T a b l e X, a difference in t h e presence of t h e polarizability t e n s o r is n o t e d (see T a b l e X b ) . S u m m a r i z i n g t h e differences f o u n d in T a b l e X b , Big species c o n t a i n t h e polarizability t e n s o r ( a ~ - a ~ ) while species B~g possesses a ~ . Of course, polarized R a m a n studies on this oriented c r y s t a l would d e t e c t this difference; however, t h e experimental results are e x t r e m e l y difficult to o b t a i n for this phase of t h e crystal. This m i s t a k e will n o t o c c u r if the p r o p e r selection is m a d e in the correlation t a b l e s ; however, the a u t h o r s felt it useful to include a n example of an i m p r o p e r choice to a c q u a i n t the r e a d e r w i t h this problem.

Table XI. Brillouin zone for simple cubic space groups, O~~ (P~8,~) (see Ref. 5).

Wyckoff's notation a b c
d

No. of equivalent positions 1 1 3


3

Coordinates of typical point in special position


x /a, y /a, z / a

(a = side of cubic cell) O, O, 0 9, 9, , , 0


9, 0, 0

Notation of BSW" for corresponding point in reciprocal space F R M


X

Type of symnmtry at corresponding point in reciprocal space Oh 0~


D4h D4h

e f
g

6 6
8

u, 0, 0 , 9, u
u, u, u

~ T
A

C4~ C4v
Car

h i j k l m
BSW =Bouckaert, Smoluehowski;

12 12 12 24 24 24
and Wigner.

, u, 0 u, u, 0 , u, u O, u, v
, u, v

Z E S W
G

C2, C~ C~ C,
C,

u, u, v

C,

APPLIED SPECTROSCOPY

163

Lattice Vibrations of Iodine Atoms. Information: I, site C4,., Z ~ = 2 (Table IV). Iodine: C~ Site symmetry species cont.aining translation A~ ~
E ~

If the correlation tables C2' --~ C2' given in Table X were used here to map D2d into D4h, the following irreducible representation would be obtained:
2~ Fr oc 'Ce -B A , + E t ' - -- g+
g

,fv t ~ '2 i(T~)


4 2(T..,)

D,~ Correlation Factor ) group


species

a~
C iat=aA~+aE

+E~

l* A,~
A.,.,,(T,)
*' Eo

1
1
2

1
1
1

1
1
0

0
0
I

E,,(T~-,v)

F1 = A 1, (") + A

2u (jr)

+ E , (R) + E . (i:)

l~...... tical = A 2,,+ E,, S u m m a r y of the lattice vibrations in the N H d crystal : (B~o+A2~+Eo+E.) iaNttd lattice rib =
+ ( A t ~ + A 2 , + E g + E ~ , ) -- (A.,.u+E~)
I ~lN a tH t i4c/e v i b = A l a ( R ) - ~ - A 2u ( i r )

+Bag (R) + 2 E g (m q-Eu (it)

6c. Librations (rotations) on the NH4 + Ion in the Crystal T h e rotations of the NH4 + ion about the x, y, or z axis have the same character as the rotations (R., Ry, and R,) contained in the character table :of the D2d site group. Therefore, the species for the librations parallel to the x, y, or z axis will be easily identifiable. T h e correlation m e t h o d is now applied to relate the librations oa the site group to the specific species of the factor group. The following slight modifications are necessary in treating librations. (1) f,'='a~E C~, (11)

Comparing the above two irreducible representations for the librations, we note the following difference. Fc~,-~c~' indicates ~ libration in species B2, while rot Fc'~c~' does not contain species B2, b u t has the rot additional species B ~ . Therefore, the representation differs in the presence (or absence) of species B2, and B ~ . Neither species B~, or B2~ is infrared or R a m a n active ; therefore, in this specific case the selection rules are unaffected b y the choice of correlation table. T h e proper choice of the correct correlation would be i m p o r t a n t in predicting the spectral activity of overtones, combinations, and difference tone where the s y m m e t r y of this libration must be correctly known. The reader is referred to Durig's p a p e # for an excellent application of deuteration studies which distinguished between the lattice vibration and the libration in tiffs crystal. 6d. Intramolecular Vibrations of NH4 Ion The correlation methods can be used again to place the different intramolecular vibrations of the NH4 + group in the proper species of the factor group. First, the n u m b e r of iutramolecular vibrations of the NH4 + ion can be obtained using Td molecular s y m m e t r y of the individual ion. The irreducible representation is FF= A i + E + 2 F 2 . Then, these molecular vibrations are correlated to the D2a site species and the site species are integrated into the factor group in the following manner. Here, to avoid clutter, each species of Ta molecular s y m m e t r y will be dealt with separately. A new column, Vvlb,is introduced which is the degree of vibration freedom of the single ion NH4 +. F o r these molecular vibrations, the following s u m m a t i o n is used
Z vvib, = 3 n - - 6 = 9 = l ( A 1 ) + 2 ( E ) - + 6 ( F 2 ) =9

where Ra~ is the degree of rotational freedom cont r i b u t e d b y ~ species of the site group. Also,
Rat = ~ Ra x.
-/

(2)

FHbratio.= ~ ~a~'~.

(12)

Of course, one notes Eqs. (11) and (12) are identical to Eqs. (2) and (6), respectively, with only the superscript R added to indicate rotation. NH~ Librations. Information : NH~--site D:a, Z" = 2 (see Table IV). D._,,tSil.e D4h symmetry Correlation Factor av species with c:' ~ c: '') group rotation species C~. a~=aA2+aE
1 1 o

also

R~ 2 ](R= 4 2(R.. v)

f 'Y ~

Z Pvib,

- ~

~ E~ E.

2 2

1 1

0 0

1 1

(1)
164

rrCg{-~c'=~ a ~ . ~ ' = A 2 g + B ~ u + E g + E . .

where Z B = n u m b e r of NH~ + molecule in the Bravais cell; therefore, f f becomes the degree of vibrational freedom in the Bravais cell. I n f o r m a t i o n Needed. NH4 + ion Td molecular symmetry, D2~--site symmetry, and D4h factor group symmetry. Z B= 2 (see Tables I and IV).

Volume 25, Number 2, 1971

Molecular symmetry
f T ~ Z " IIv ib ~vib

Correlation )

Site symmetry
D~d
al

Correlation

Td

C~
1

a i-

Cg ~ C:"

D4h Factor group species

Cr
1 1 1

a i-

2 4

1 2

A~

22

A,~
B2~

I 1 l l l l

B2.
B, 1 2 1 2 4 4 ~ ~ ~ ~

1 1 1

i2

A,,,
E~ Eu(T~.v ) B~,, A2~(Tz)

B,g

F2

E B..,

2 2
1 1

2 2
2 2

The irreducible representation and spectral a c t i v i t y can be s u m m a r i z e d in the following manner. Trans- AcousCrystal lations tical symmetry (lattice vibraD~ vibration) tion Azo 1 A~u B,g
Bag

Rotation Intra(libra- molecular tion) vibration 1 1


2

Spectral activity D4h


R

1
2

' R R
*

Eg

A~ 1 1 2 B,~ 1 0 B~ 2 E~ 1 1 1 2 Final check: Total vibrations (3N)=9+3+6+18=36, N=12.

Azu

ir ir where

II. GENERAL APPLICATION OF CORRELATION METHOD


T h e authors and friends h a v e successfully applied the basic procedure presented herein to m a n y crystals. Only ionic t y p e crystals have been t r e a t e d in this p a p e r ; however, no problem was encountered in predicting the selection rules for graphite, diamond, and polyethylene. T h e b e a u t y of this m e t h o d lies in the basic application of simple principles in group theory. T h e only errors which can occur will be our own. T h e authors feel t h a t this method adds still another degree of e n j o y m e n t in doing molecular spectroscopy !

points in the Brillouin zone and m u s t be considered in the irreducible representation for these points in reciprocal space. T a b l e X I gives a description of the Brillouin zone nomenclature for the cubic space group 0h 1 and the notation for the corresponding points in reciprocal space is shown in Fig. 1. To obtain the irreducible representation for some point in reciprocal space, we need only to correlate the lattice vibrations occurring in the site group species to the t y p e of s y m m e t r y at the corresponding point in reciprocal space; a typical example of these s y m m e t r i e s is given in T a b l e X I for the cubic space groups 0h 1. N o w the acoustical vibrations are not s u b s t r a c t e d f r o m the irreducible representation, but m u s t be included because of their nonzero frequencies. T h e selection rules for ir and R a m a n activity of f u n d a m e n t a l vibrations, acoustical vibrations, overtones, different tones, and combinations are determined f r o m the point s y m m e t r y group in reciprocal space. Care must be exercised in this application.

III. SELECTION RULES FOR k ~ O


Previously, we have discussed only those selection rules for the center of the Brillouin zone, i.e., k = O . At this boundary, k = 0, the acoustical vibrations were disregarded because of their near-zero frequency. T h e acoustical vibrations are not near zero at other

FIG. 1. The Brillouin zone for 0hi(Presto). Noiations from Bouckaert, Smoluehowski, and Wigner. Side of the cube equals 1/a (Ref. 5).

APPLIED SPECTROSCOPY

165

ACKNOWLEDGMENTS
First, we wish to thank Professor Jim Durig for his patient instructions in the basic details of the correlation method. Many useful discussions with Dr. G. L. Carlson, Dr. R. J. Van Dyke, Professor William White, and Professor Foil A. Miller have encouraged us to write this review paper, adding modifications at points which appeared to need clarity. One of the authors (W. G. F~teley) wishes to acknowledge the partial support of Air Force Contract No. F33615-70-C-1382 and Mellon Institute.

APPENDIX I

Site Symmetry Table for Bravais Space Cell


The following table was compiled from the site symmetry tables for crystallographic groups found in the International Tables for X-Ray Crystallography, Vol. I. Please note that the table is modified and should only be used for the Brav~is space cell and the Halford site symmetry correlation method suggested in this article. The site symmetries are arranged in alphabetical order reading from left to right. See Appendix II for an explanation of this ordering.

Space group
1 P1 C, ~ C1(1)

Site symmetries C~' C2' C~2 C~~ C. ~ C~~


C~~ C, 4

Space group 58 P n n m 59 P m m n 60Pbcn 61 Pbca 62 P u m a 63 C m c m 64 Cmca 65 C m m m 66 Cccm 67 C m m a 68 Ccca 69 F m m m 70 F d d d 711mmm 72 I b a m 73 Ibca 74 I m m a 75 76 77 78 79 80 8l 82 83 P4 P4, P4~ P4a 14 I4, P4 I4
P4/m

Site symmetries
D2h 1~ 4C2h(2) ; 2C2(4) ; C~(4) ; CI(8) D2h TM 2C2. (2) ; 2Ci(4) ; 2C~ (4) ; C1 (8)

2 3 4 5 6 7
8 9

10 11

PI P2 P2, B~ or C~ Pro" Pb or Pc B m or C m Bb or Cc P2/m P2,/m

8C~(1) ; C,(2) 4C2(1) ; C,(2) C, (2) 2C~ (1); C, (2) 2C~ (1) ; C, (2) C,(2) C,(1) ; C,(2)
C,(2)

D2h '4

2Ci(4);C2(4);C,(8)

D2h 15 2C~(4) i C1(8) D~h16 2Ci(4) ; C. (4) ; C~(8) D~h 1~ 2C2h(2) ; C2v(2) ; Ci(4) ; C2(4) ;

2C~(4) ; C~(8) D~h TM 2C2h (2) ; Ci(4) ; 2C2(4) ; C~(4) ; C,(8) D2h 1~ 4D2h (1) ; 2C~h(2) ; 6C2.(2) ; C2(4) ;

C~' C~ ~
C:~ ~

12B2/morC2/m

8C2~(1) ; 4C~(2) ; 2C.(2) ; C,(4) 4C~(2) ; C~(2) ; C,(4) 4 C ~ ( 1 ) ; 2 C i ( 2 ) ; 2 C ~ ( 2 ) ; C,(2); 4C~ (2); 2C~(2) ; C, (4) 4Ci(2) ; C,(4) 4C~ (2) ; C~ (2) ; C, (4) 8D~(1) ; 12C2(2) ; C~(4) 4C~ (2) ; C1 (4) 2C~(2) ; C~(4) C1 (4) 2C2 (2) ; C, (4) 4D2(1) ; 7C~(2) ; C~(4) 4D~(1) ; 6C~(2) ; C~(4) 4D~(1) ; 6C~(2) ; C~(4) 3C~ (2) ; C1 (4) 4C~(1) ; 4C.(2) ; C~(4) 2C.(2) ; C~(4) 4C~(2) ; C1(4) 2C~ (2) ; C~ (2) ; C, (4) C, (4) 2C~(2) ; C,(4) C, (2) ; C, (4) 2C~ (2) ; C, (4) C,(4) 2C~(2) ; C,(4) 2C~(1) ; C~(2) ; 2C.(2) ; C,(4)
3C~ (2) ; C, (4)

4C~(4) ; C, (8)
C, (8)
2C~(4) ; C,(8)

D2h 2o 2D~(2) ; 4C~(2) ; 5C~(4) ; C.(4) ; D~h21 2D2(2) ; 4C~ (2) ; C2~ (2) ; 5C2(4) ; D2h ~ 2D~(2) ; 2Ci(4) ; 4C~(4) ; C1(8) D2n 23 2D2h (1) ; 3C2h (2) ; D2(2) ; 3C~(2) ;

13 P 2 / b or P 2 / c ., 14 P 2 , / b or P 2 , / c 15 B 2 / b or C 2 / c 16 P222 17 P222, 18 P2,2~2 19 P2~2~2~ 20 C222, 21 C222 22 F222 23 I222 24 I2~2,21 25 Prom2 26 Pmc2~ 27 Pcc2 28 Pma2 29 Pea% 30 Pnc2 32 33 34 35
31 Pmn2~ Pba2 Pna2~ Pnn2 Cram2

C2h4
C2~~ C~ ~

C, (4)

D~' D2 ~ D2 ~ D~~ D2 ~ D26 D~ ~ D2 s D2 ~


C~. ~ C~.~ C2~3

3C2(4) ; 3C~(4) ; C~(8)


D2h 2~ 2D2(2); 2C(4); 3C:(4); C,(8) D2h 25 4 D ~ h ( 1 ) ; 6 C 2 ~ ( 2 ) ; C i ( 4 ) ; 3 C . ( 4 ) ;
D2a 2~ 2D~(2) ; 2C~(2) ; Ci(4) ; 4C~(4) ;

C,(8)

c~(4) ; c~(8)
D~ ~

2Ci(4) ; 3C~(4) ; C,(8) D ~ 2s 4C~ (2) ; C2~(2) ; 2C2(4) ; 2C,(4) ;

C, (8)

C~ 4
C~ ~ C~v~ C2J

C~ s
C~ ~ C~ ~ C2. u

C,' C, ~ C4~ C44 C~~ Ca ~ $4 ~ $42

C4~'
C~ ~
Cab3 C~a~ C~ ~ C~h~

37 Ccc2 38 A t o m 2 39 A b m 2 40 A r e a 2 41 A b a 2 42 From2 43 F d d 2 44 I m m 2 45 Iba2 46 I m a 2 47 P m m m 48 P n n u 49 Pccm 50 Pban 51 P m m a 52 53 54 55 56 57


Pnna Pinna Pcca Pbam Pccn Pbcm

36 Cmc2~

C~o ~ C,(2); C1(4)


C ~ 13

84 P4~/m 85 P 4 / n 86 P 4 ~ / n 87 I 4 / m 88 I 4 ~ / a 89 P422 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 P42~2 P4,22 P4~2~2 P4222 P4~2,2 P4a22 P4~2,2 422 I4~22
P4mm P4bm P42cm

2C4 (1) ; C~ (2) ; C, (4) C,(4) 3C~(2) ; C,(4) C, (4) C4(1) ; C~(2) ; C1(4) C2(2) ; C,(4) 4S4(1) ; 3C2(2) ; C,(4) 4S4(1) ; 2C~(2) ; C,(4) 4C4~(1) ; 2C~(2) ; 2C4(2) ; C2(4) ; 2C~ (4) ; C, (8) 4C~(2) i 2S~(2) ; 3C2(4) ; C~(4) ; 2S~(2) ; C4(2) ; 2C~(4) ; C~(4) ; C,(8) 2S~ (2) ; 2C~ (4) ; 2C~ (4) ; C, (8) 2 C ~ (1) ; C2a (2) ; S~ (2) ; C~ (2) ; el(4) ; C2(4) ; C.(4) ; C,(8) 2S4(2) ; 2Ci(4) ; C~(4) ; C~(8) 4D4(1) ; 2D~(2) ; 2C4(2) ; 7C~(4) ; 2D:(2) ; Ca(2) ; 3C2(4) ; C~(8) 3C~(4) ; C~(8) C2(4) ; C~(8) 6D~ (2) ; 9C~ (4) ; C, (8) 2D~(2) ; 4C~(4) ; C1 (8) 3C~(4) ; C,(8) C:(4) ; C,(8) 2D4(1) ; 2D~(2) ; C4(2) ; 5C~(4) ; 2D~(2) ; 4C~(4) ; C,(8) 2C4,(1) ; C2~(2) ; 3C~(4) ; C1(8) C~(2) ; C~.(2) ; C.(4) ; C~(8) 2C~(2) ; C~(4) ; C.(4) ; C~(8) C~(2) ; C~(4) ; C.(4) ; C~(8) 2C4(2) ; C~(4) ; C,(8) C4(2) ; C2(4) ; C~(8)

C1(8)

2C~(1) ; 3C.(2) ; C~(4) 2C~(2) ; C.(2) ; C,(4) C~(2) ; C.(2) ; C~(4) C2(2) ; C~(4) Car TM C~,(1) ; C~(2) ; 2C.(2) ; C1(4) C~.~ C~(2); C~(4) C2,,2o 2C~.(1) ; 2C,(2) ; C~(4) C~,,2' 2C~(2) ; C,(4) C ~ 2~ C~(2) ; C.(2) ; C~(4) D~a~ 8D~h(1); 12C~,(2) ; 6C~(4) ; C1(8) D,a ~ 4D~ (2) ; 2C~ (4) ; 6C~ (4) ; C, (8) D2a~ 4Cab (2) ; 4D2 (2) ; 8C, (4) ; C. (4) ;
C~. '~ C~. '~ C~,,'~ D~ ~ D~n ~ D~ ~ D~a~ D:~ ~ D2~ ~ D2~ ' D~ u

C2v'4

D4' D~2 D~ ~ Da ~ D4 ~ D4 ~ DJ D4 s
D49

C,(8)

4D~(2) ; 2C~(4) ; 6C~(4) ; C,(8) 4C~a(2); 2C2~(2); 2C2(4); 3C.(4); 2C~(4) ; 2C~(4) ; C,(8) 4C~(2) ; 3C~ (4) ; C, (4) ; C1 (8) 2C~(4) ; 3C~(4); C~(8) 4 C ~ (2) ; 2C~(4) ; 2C.(4) ; C~(8) 2C~(4) ; 2C~(4) ; C~(8) 2C~(4), C~(4) ; C~ (4) ; C, (8)

C, (8)

C,(8)

Da ~0
C4~,1 CaJ C4J

C,(8)

P4~nm
P4cc P4nc

C~ ~
C~ 5 C4~~

166

Volume 25, Number 2, 1971

Space group 105 P4~mc 106 P4~bc 107 I4mm 108 I4cm 109 I4m~d 110 I4.cd 111 P 4 2 m 112 113 114 115 PY~2c P.~2~m P42~c pTtm2 C4, s C4~~ C4~1 C4~n C4~'~ D~a ~ D~.? D~ a D2d 4 D~a ~ D~d ~ D~d ~ D~d s D~d~

Site s y m m e t r i e s

Space group 159 160 161 162 P31c R3m R3c P31m

Site s y m m e t r i e s

C4j

2C~(4) ; C~(8) C4~(1) ; C~(2) ; 2C~(4) ; C~(8) C4(2) ; C~(2) ; C~(4) ; C~(8) C2~ (2) ; C~ (4) ; C~ (8) C~(4); C,(8) 4 D ~ (1) ; 2D~(2) ; 2C~(2) ; 5C~(4) ; C~ (4) ; C~ (8) 4D2(2) ; 2S4(2) ; 7C~(4) ; C.(8) 2S4(2) ; C~,(2) ; C2(4) ; C.(4) ; C1(8) 2S4(2) ;2C~(4) ; C~(8) 4D~a (1) ; 3C~,(2) ; 2C~(4) ; 2C~(4) ;

3C~(2) ; 2C~(4) ; C~(8)

c~v 4 c~ ~ c~ ~ Dad'
D3a 2 D3a 3 D3~ 4

163 P31c 164 P 3 m l 165 P 3 c l 166 R3m 167 R3c 168 169 170 171 172 173 174 175 P6 P6~ P6~ P6~ P64 P6~ P6 P6/m

116 pTic2 117 PY~b2 1.18 PY~n2 119 I4m2

C~(8)
2D~(2) ; 2S4(2) ; 5C~(4) ; C,(8) 2S4(2) ; 2D~(2) ; 4C(4) ; Ct(8) 2S4(2) ; 2D2(2) ; 4C~(4) ; C1(8) 4D2~(1) ; 2C~(2) ; 2C2(4) ; C~(4) ;

D3d5
D3e 6

C~ (8)
120 I4c2 121 I42m
122 142d 123 P 4 / m m m 124 P4/mcc 125 P4/nbm 126 P4/nnc 127 P4/mbm 128 P4/mnc ]29 P4/nmm 130 P4/ncc 131 P4~/mmc 132 P4~/mcm 133 P42/nbc 134 P4~/nnm 135 P4~/mbc 136 P4~/mnm i37 P42/nmc 138 P4~/ncm 139 I 4 / m m m 140 I4/mcm 141 I4,/amd 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 D2d ~o D~(2) ; 2S4(2) ; D~(2) ; 4C~(4) ; C 1 ( 8 ) D~an 2 D ~ ( 1 ) ; D~(2) ; $4(2); Car(2) ; 3Cz(4) ; C~(4) ; C,(8) D~a '~ 2S4(2) ; 2C~(4) ; C~(8) D ~ ~ 4D4~ (1) ; 2D~a (2) ; 2C4~(2) ; 7C2.(4) ; 5Cs (8) ; C1 (16) D4a~ D4 (2) ; C4~ (2) ; D4 (2) ; C4a (2) ; C~a(4) ; D2(4) ; 2C4(4) : 4C2(8) ; C~(8) ; C~(16) D4~~ 2D4(2) ; 2D~a(2) ; 2C~a (4) ; C4(4) ; C~.(4) ; 4C~(8) ; C~(8) ; C~(16) Dab4 2D4 (2) ; D~ (4) ; $4 (4) ; C4 (4) ; C~ (8) ; 4Ce(8) ; C~(8) D~a ~ 2C4~ (2) ; 2 D ~ (2) ; C~(4) ; 3C~(4) ; 3C~(8) ; C~(16) D ~ ~ 2C4~ (2) ; C ~ (4) ; D2 (4) ; C4 (4) ; 2C2(8) ; Cs(8) ; C1(16) D4J 2D~a(2) ; C4~(2) ; 2C2a (4) ; C~(4) ;

C61 C6~ C63 C64 C65 C66 Cab ~ C6h~


C6h~ D61 D62 D6 a D64 D6 ~ D66 C6~~
C6. ~ C~ a C~ 4 D~hI

176 P6a/m 177 P622 178 179 180 181 182 183 184 185 186 187 P6~22 P6~22 P6222 P6422 P6~22 P6mm

2c~(8) ; 2c~(8) ; c~(16)


D~ s D~ 9
D4hI

D~(4) ; $4(4) ; C4(4) ; Ci(8) ; 2C~(8) ; C, (16) 4D~(2);2D~(2);7C~(4);C~(8); 3C~(8) ; C,(16) D~h (2) ; D~d(2) ; D~h (2) ; D~a(2) ; D2(4) ; C~h (4) ; 4C~,(4) ; 3C~(8) ;

P6cc P63cm P6amc P6m2

188 P6c2 189 P 6 2 m 190 P62c 191 P 6 / m m m 192 P6/mcc 193 P6~/mcm 194 P6~/mmc 195 P23 196 197 198 199 200 F23 I23 P2~3 I2,3 Pm3

D~h~
D~ a D~ 4 D~a I D6~~ D~ 3 D6~ ~ T~ T~ T3 .7TM T~ T~ ~ T~~ T~ ~ Ta 4 Ta b Th ~ T~ ~ 0~ 0~

2C~(8) ; C,(16)

D~fl ' 3 D : ( 4 ) ; $ 4 ( 4 ) ; C ~ ( 8 ) ; 5 C ~ ( 8 ) ; C ~ ( 1 6 ) D4~ 1~ 2 D e ~ ( 2 ) ; 2 D ~ ( 4 ) ; 2 C ~ ( 4 ) ; C 2 " ( 4 ) ; 5C~(8) ; C~(8) ; C,(16) D4~ ~ C ~ ( 4 ) ; S ~ ( 4 ) ; C ~ ( 4 ) ; D ~ ( 4 ) ; 3C2(8) ; C.(8) ; C1(16) D4~ TM 2D2~(2); C~h(4); $4(4); 3 C ~ ( 4 ) ; C~(8) ; 2C~(8) ; C~(16) D~a ~ 2 D 2 ~ ( 2 ) ; 2 C ~ , ( 4 ) ; C ~ ( 8 ) ; C ~ ( 8 ) ;

C~(8) ; C~(16)
D ~ ~6 D ~ ( 4 ) ; $ 4 ( 4 ) ; 2 C 2 ~ ( 4 ) ; C 2 ~ ( 4 ) ;

I4~/acd P3 P3~ P3~ R3 P3 R3 P312 P321 P3112 P3~21 P3212 P3~21 R32 P3ml P31m P3cl

3c~(8) ; c.~(8) ; c,(16) D4h~7 2D~h(1) ; D ~ (2) ; D ~ ( 2 ) ; C4v(2) ; C ~ (4) ; 4C~, (4) ; C~ (8) ; 3C~ (8) ; C~ (16) D ~ ~s D4(2); D ~ ( 2 ) ; C4~(2); D ~ ( 2 ) ; C~ (4) ; C4 (4) ; 2C~, (4) ; 2C~ (8) ; 2C~(8) ; C,(16) D ~ 19 2 D ~ d ( 2 ) ; 2 C ~ ( 4 ) ; C ~ ( 4 ) ; 2 C ~ ( 8 ) ; Cd8); C,(16) D~a ~ $ 4 ( 4 ) ; D ~ ( 4 ) ; C ~ ( 8 ) ; 3 C ~ ( 8 ) ; C 1 ( 1 6 ) C3~ 3C3(1) ; C4(3) C~2 C~ (3) C. ~ C~ (3) c~4 c~ (1); c~(3) C3~~ 2C,~(1) ; 2C~(2) ; 2C~(3) ; C~(6) C37 2C,~(1) ; C,(2) ; 2C~(3) ; C1(6) Da ~ 6D, (1) ; 3C~ (2) ; 2C~(3) ; C~(6) D3 ~ 2D3 (1) ; 2C~ (2) ; 2C~(3) ; C1(6) D~ ~ 2C~(3) ; C~(6) D34 2C: (3) ; C~ (6) Da 5 2C~(3) ; C~(6) D, 6 2C~(3) ; C~(6) D3 ~ 2Da(1) ; C3(2) ; 2C~(3) ; C,(6) C3~~ 3C~(1) ; C.(3) ; C~(6) C.~~ C~(1) ; Cs(2) ; C,(3) ; C1(6) C~" 3C3(2) ; C~(6)

201 P n 3 202 Fro3 203 Fd3 204 Im3 205 P a 3 206 Ia3 2O7 P432 208 P4~32

2c~(2); c,(6) c~v(1); c,(3); c,(6) c,(2); c~(6) 2D~a(1) ; 2D3(2) ; C3~(2); 2C2h (3) ; C3(4) ; 2C2(6) ; C~(6) ; C1(12) D3 (2) ; C31 (2) ; 2D3 (2) ; 2C~ (4) ; C~(6);C~(6);C1(12) 2D3d(1) ; 2C3~(2) ; 2C2h (3) ; 2C2(6) ; c~(6) ; c1(12) D~ (2) ; C3~(2) ; 2C3 (4) ; Ci(6) ; C2(6) ; C~(12) 2D3d(1) ; C ~ (2) ; 2C2h (3) ; 2C~ (6) ; c,(6) ; c,(12) D~ (2) ; C3~(2) ; C3 (4) ; C~(6) ; C2(6) ; C, (12) C6(1) ; C3(2) ; C2(3) ; C,(6) C~(6) C1 (6) 2C~ (3) ; C~ (6) 2C2(3) ; C1(6) 2C~ (2) ; C, (6) 6C3h(1) ; 3C3(2); 2C.(3) ; C1(6) 2C6h(1) ; 2Cob (2) ; C6(2) ; 2C~h (3) ; C3(4) ; C2(6) ; 2C~(6) ; C~(12) C3a(2) ; C3~ (2) ; 2C3h (2) ; 2C3 (4) ; C~(6) ; C~(6) ; C~(12) 2D6(1) ; 2D3 (2) ; C6(2) ; 2D~(3) ; c,(4) ; 5c2(6) ; C~(12) 2C~(6) ; C1(12) 2C2(6) ; C1(12) 4D~(3) ; 6C2(6) ; C~(12) 4D~(3) ; 6C~(6) ; C,(12) 4Da (2) ; 2C:. (4) ; 2C:(6) ; C1 (12) Car(l) ; C3v(2) ; C ~ ( 3 ) ; 2C~(6) ; C~(12) C6(2) ; C~ (4) ; C~(6) ; C~ (12) C.~(2) ; C~(4) ; C~(6) ; C,(12) 2C~(2) ; C~(6) ; C~(12) 6 D ~ ( 1 ) ; 3Ca~(2); 2C2,(3) ; 3C,(6) ; C1(12) D~ (2) ; C:~ (2) ; D~ (2) ; C~ (2) ; Da (2) ; C~(2) ; 3C~(4) ; C~(6) ; C~(6) ; C,(12) 2 D ~ ( 1 ) ; 2 C ~ ( 2 ) ; Ca~(2); 2C~.(3); Ca(4) ; 3C~(6) ; C~(12) D~ (2) ; 3C~ (2) ; 2C~ (4) ; C2 (6) ; C~(6) ; C~(12) 2D6~ (1) ; 2D~a (2) ; C~(2) ; 2 D ~ (3) ; C~(4) ; 5C~v(6) ; .4C~(12) ; C~(24) D6(2) ; C6h(2) ; D~(4) ; C ~ (4) ; C~(4) ; D~ (6); C~ (6); C~ (8); 3C~ (12); C~(12) ; C,(24) D ~ (2) ; D~d(2) ; C.~(4) ; D3 (4) ; C6(4) ; C ~ (6); C~v(6) ; CC,(8) ; C~(12) ; 2C~(12) ; C, (24) D ~ (2) ; 3 D ~ (2) ; 2C~(4) ; C2~ (6) ; C~(6) ; C~(12) ; 2C~(12) ; C~(24) 2T(1) ; 2D~(3) ; Ca(4) ; 4C~(6) ; C~ (12) 4T(1) ; C~(4) ; 2C~(6) ; C~(12) T ( 1 ) ; D~(3); C~(4); 2C~(6); C1(12) C~ (4) ; C~(12) C~(4) ; C~(6) ; C~(12) 2T~(1) ; 2 D ~ (3); 4C~,(6) ; Ca(8) ; 2C.(12) ; C. (24) T(2) ; 2C.~(4) ; D:(6) ; C~(8) ; 2C~(12) ; Ct (24) 2T~(1); T ( 2 ) ; C~ (6) ; C~(6) ; C~(8) ; C~(12) ; C~(12) ; C1(24) 2 T ( 2 ) ; 2C~(4) ; C~(8) ; C~(12) ; C~(24) T~(1) ; D ~ (3) ; C~i(4) ; 2C2,(6) ; C~(8) ; C.(12) ; C,(24) 2C~i(4) ; C~(8) ; C1(24) 2Ca~(4) ; Ca(8) ; C2(12) ; C~(24) 20(1) ; 2D4(3) ; 2C4(6) ; C~(8) ; 3C~(12) ; C~(24) T (2) ; 2Da (4) ; 3D~ (6) ; C~ (8) ; 5C~(12) ; C~(24)

APPLIED SPECTROSCOPY

167

Space group 209 F432 210 F4~32 211 432 212 P4~32 213 P4~32 214 14,32 215 PY~3m 216 F43m 217 143m 218 p743n 219 F3~3c 220 I7~3d 221 Pm3m 0~ 0~
0~

Site symmetries 20(1); T(2); D~(6) ; C~(6) ; C~(8) ; 3C~(12) ; C~(24) 2T(2) ; 2D~ (4) ; C~(8) ; 2C~(12) ; CC~ (24) O(1);D,(3);Da(4);D~(6);C~(6); Ca(8) ; 3C~(12) ; C~(24) 2Da(4) ; C~(8) ; C~(12) ; C~(24) 2D~ (4) ; C~(8) ; C~(12) ; C~(24) 2D~(4); 2D~(6) ; Ca(8) ; 3C~(12) ; Ct (24) 2To(l) ; 2D~(3) ; C~(4) ; 2C~(6) ; C~(12) ; C,(12) ; Ct (24) 4Ta(1) ; C**(4) ; 2C~(6) ; C,(12) ; C~(24) T~ (1) ; D:~ (3) ; C~. (4) ; S~ (6) ; C~(6) ; C~(12);C,(12);C1(24) T (2) ;D, (6) ; 2S~ (6) ; C~(8) ; 3C~(12) ; C~(24) 2T(2) ; 2S, (6) ; C~(8) ; 2C~(12) ; C~(24) 2S~(6); C~(8) ; C~(12) ; C~(24) 20a (1) ; 2D~a(3) ; 2C**(6) ; Ca~(8) ; 3C~,(12) ; 3C~(24) ; C~(48)

Space group 222 Pn3n 223 Pm3n 224 Pn3m 225 Fm3m 226 Fm3c 227 Fd3m 228 Fd3c 229 Im3m 230 Ia3d

Site symmetries Oa~ 0a a 0~~ O~~ Oa~ 0~


O~ s

0~ 0~ 0s T~~ T~~ T~~ Td4 Ta ~ T~~ O~~

0(2) ; D4(6) ; Cai(8) ; $4(12) ; C~(12) ; Ca(16) ; 2C~(24) ; C~(48) T~ (2) ; D~ (6) ; 2D~ (6) ; D.~(8) ; 3Cz,(12) ; Ca(16) ; C~(24) ; C~(24) : C~(48) T~(2) ; 2D~(4) ; D~ (6) ; C~,(8) ; D~(12) ; C~(12) ; 3C~(24) ; C~(24) ; C~(48) 20~(1); Td(2); D~(6); Car(6) ;, C~,(8) ; 3C~,(12) ; 2C~(24) ; C~(24) ; C~(48) 0(2); T~(2); D~,~(6); C~(6) ; C~,(12) ; C~(12) ; C~(16) ; C~(24) ; C~(24) ; C~(48) 2T~(2) ; 2D~(4) ; C~,(8) ; C~,(12) ; C,(24) ; C~(24) ; C~(48) 2C~(24) ; C~(48) 0~ (1) ; D~ (3) ; D~ (4) ; D~,~(6) ; C4~(6) ; Ca,(8) ; 2C~v(12) ; C~(24) ; 2C~ (24) ; Ct (48) C~(8) ; Da(8) ; D~(12) ; $4(12) ; C~(16) ; 2C~(24) ; C,(48)
T (4) ; D~ (8) ; C~ (8) ; S~ (l 2) ; Ca (16) ;

0~9 O~TM

N o t e t h e following e q u i v a l e n t n o m e n c l a t u r e s : C~ ~ $2; C~-=Clh; D 2 ~ V ; D 2 h ~ V h ; D 2 d ~ V d ; C~i------S6. Site in Appendix I


APPENDIX Site II

Alphabetical order D2~(2) D~d(2) C~h(4) C2h(4) C~,(4) C2(8) C~(8) C,(8) C,(16)

Alphabetical ordering of site position a b c d c f g h i

Atom (site) ~ Ti (a)

2D2d(2) 2C~h(4) C2,(4) 2C2(8) C~(8) C,(I6)

Symmetry

T h e first e x a m p l e t h a t h a d an a m b i g u o u s choice of ~he site s y m m e t r y was t h e e q u i v a l e n t set of o x y g e n a t o m s in Ti02. Recalling f r o m t h e x - r a y i n f o r m a t i o n t h a t four e q u i v a l e n t o x y g e n a t o m s are present in the B r a v a i s cell, this e q u i v a l e n t set could be placed either on C2~(4) or C2~(4) sites. A c t u a l l y t h e W y c k o f f tables s on t h e published c r y s t a l l o g r a p h i c d a t a indicate t h e site position of each e q u i v a l e n t set of a t o m s in t h e following notation.
Wyckoff's Tables for TiO2.

()xy (e)

I n f o r m a t i o n from Wyckoff's table, and the references.

Atom Ti Oxygen

Site Position (a) 0, 0, 0; 0, b, (e) 0,0, u ; 0 , 0 , ~ ; 0 , , u+; 0, , - u

One could consult t h e c r y s t a l l o g r a p h i c tables 7 and i d e n t i f y t h e site f r o m t h e x, y, z coordinates ; however, a m u c h simpler p r o c e d u r e can be followed. A p p e n d i x I presents the site s y m m e t r y in t h e alphabetical order in t h e following m a n n e r . Using TiO2 as a n example, A p p e n d i x I gives for D4h~9: 2 D ~ ( 2 ) , 2C2h(4), C2~(4), 2C2(8), C~(16). N o t i n g t h a t D2d, C2h, and C: a p p e a r twice, one c a n write f r o m the d a t a in A p p e n d i x I the following alphabetical ordering.

T h e alphabetical letter in t h e parenthesis following Ti in W y c k o f f ' s table indicates t h e site of t h e a t o m , i.e., (a) indicates t h e t i t a n i u m is on site D2d. F o r t i t a n i u m , this could h a v e been d e t e r m i n e d b y p r e v i o u s c o n s i d e r a t i o n s ; however, t h e site position of the f o u r e q u i v a l e n t o x y g e n a t o m s a p p e a r s to leave one the choices of either C2h(4) or C2~(4) sites for, as n o t e d before, b o t h sites will a c c o m m o d a t e f o u r e q u i v a l e n t atoms. W y c k o f f ' s tables give the position of the o x y g e n a t o m s ou an (e) site. N o t i n g t h e alphabetic t a b u l a t i o n of sites a b o v e shows t h a t the (e) site is C2v. Therefore, there is no a m b i g u i t y in the choice of site position for atoms, molecules, or ions if all t h e i n f o r m a t i o n given in c r y s t a l l o g r a p h i c tables is p r o p e r | y used. A n o t h e r example of the p r o p e r use of t h e crystallographic i n f o r m a t i o n is the a-A120a crystal which is R~c=--D:~ ~, Z = 2 . C o n s u l t i n g A p p e n d i x I for D3d 6, we find D3(2), C3~(2), C3(4), C~(6), C2(6), C1(12). Ob-

168

Volume 25, Number 2, 1971

viously the four equivalent aluminum atoms can only be accommodated on the C~(4) site. However, the six equivalent oxygen atoms might be located in either the C~(6) or C2(6) site. Wyekoff's table gives the following information for c~-A1203: A1 Oxy Site (c) (e).

O
O F1G. 2. Unit cell of SrTiO~. . = T i Sr = strontium.

Therefore, using the tables in Appendix I with the sites arranged in alphabetical order proceeding from left. to right, the following tabulation is implied. Site in Appendix I" D3(2) C~i(2) C3(4) Cd6) C~(6) C~(12) Alphabetical order a b c d e f

atom; O = 0

atom ;

Atom (site) Aluminum (c) Oxygen (e)

The angle 0 is defined as follows" (1) (2) (3) (4) (5) where E is a proper rotation, 0 = 0 (-t-) used for proper rotations, Cp, O= 360/P ( - ) used for improper rotations, Sp, 0 = 3 6 0 / P h is an improper rotation with 0 = 0 i is an improper rotation with 0 = 180 .

These two examples illustrate the point t h a t it is a simple m a t t e r to determine the site s y m m e t r y of an atom, molecule, or ion in a crystal lattice from information provided by x-ray experiments. Again, it is to be noted t h a t all the sites are arranged in alphabetical order in Appendix I. The table in Appendix I is similar to t h a t provided b y Adams, 9 except for two major changes : (1) A reduction in the n u m b e r of atoms found in the Bravais cell site from t h a t given for the sites of the crystallographic cell; and (2) the arrangement of the site in alphabetical order to be consistent with the crystallographic tables.

Next, each individual operation is considered in obtaining OOR and X~. Crystallographic information for SrTiO~, a perovskite, is 0h t - Pm3m. First the crystal structure with atoms in the position of the unit cell must be considered. This same unit cell shown below will be used through this discussion. I t has been prev!ously noted t h a t SrTiO~, a perovskite, is 012--Pm3m. A unit cell of this crystal structure is shown in Fig. 2. N o t e : (1) Each Ti is shared by 8 St; (2) There are 12 oxygens around 1 St. To cheek this: A lore T i - - 8 per cell, each contributing ~ to the unit cell . ' . 8 X ~ = Oxygen--12 atoms, each oxygen contributed to unit cell . ' . 1 2 X ~ = S~1 atom in middle of cell .'. 1 S r - - a t o m per unit cell Total ooR= for Z = 1 (1) E Operation. Character and n u m b e r of atoms invariant under E operation can be found as follows. All the atoms remained unchanged, .'.oOR=5 (i.e., 1 S r + l T i + 3 O). X p = 5 ( + 1 - t - 2 cos0) = 5 . 3 = 15. (2) C3 Operation. Figure 3(a) below shows the '~ axes passing through this unit cell. The following list gives a tabulation of the n u m b e r of atoms left invariant under all the C~ operations and the irreducible representation xp. coR 1Ti 30 1 Sr SrTiOz

APPENDIX III

The Method Suggested by Bhagavantan and Venkatarayudu for Obtaining the Irreducible Representation of a Crystal
Since SrTi03 has previously been treated by the correlation method, it would be worth repeating this calculation using the method proposed by Bhagavantan and V e n k a t a r a y u d u 3 to see (1) if both these methods give the same result and (2) demonstrate the simplicity of the correlation method. Only a simple outline of the B h a g a v a n t a n and V e n k a t a r a y u d u is given below. (For a complete analysis, see Ref. 3.) The irreducible representation for this crystal can be obtained as follows. B y definition wa = number of atoms left invariant under operation R. x p = t h e character of the operation R, obtained in the following manner. xp = ~0R(::t=1-1-2 cos0)

APPLIED SPECTROSCOPY

169

There are 7C~'s passing Fig. 3(a); all are parallel the 8C~ operation which table, but only one of these
Operation 'C~ ~C~ ~C~ ~C~ ~C~ C~ ~C~

through the unit shown in to each other (this is not appears in the character eight operations).
No. of atoms invariant, oo~ 1 S r + 2 . ~ Ti ~ Ti ~ Ti ~ Ti ~ Ti ~ Ti ~ Ti Total atoms 1 S r + l Tr

There is a center of s y m m e t r y at each and every atom in the unit; .'. all the atoms remain invariant under one of the m a n y /-inversion operations, i.e., 1 S r + l T i + 3 O, for Z ~ R = 5 . The $4 operation yields the same result as the C4 operation even though there is the additional reflection. If we note t h a t there are three reflection planes in the unit cell and all the atoms lie on one of these reflection planes and the $4 axis, .'. WR= 3. See Fig. 3 (e) Figure 3 (f).
Operation WR I S r + 2 . ~ Ti

.'. 2koe = 2 However, for all C~ operations


0= 120) = 0 .'.OaR(I--I-2 COS0)=0.

1+2cos0

(where

Since the above example illustrates the procedure followed on each s y m m e t r y operation, only the basic essentials are presented in the discussion below for obtaining ~a and x~ for each operation. Figure 3 (b).
Operation 'C~ ~C~ "C~ 4C~ ~C~ ~C~ ~C~ 9Ce No. of atoms invariant, WR 1 Sr+2.0 0 ~O 2. ~ Ti ~ Ti ~ Ti 2- ~ Ti ~ Ti ~ Ti Total a t o m s = l S r + l O + 1 Ti
. ~o2a = 3

1S6 ~Ss 3S 6 ~S6


~$6 6S 6 ~$6
. ~ W R = 2

Ti
-~ Ti Ti Ti Ti

I n Fig. 3 (g) all atoms are invariant under z .'. ~ R = 5. Figure 3 (h).
Operation lo'd 2O~d 3ad (O~R 2.~ T i + ~ O 4-~ T i + 2 . ~ O + S r 2-~ T i + ~ O

. ~R=3(Ti+Sr+O) The results from above can be summarized in the following table :
Species
WR X~

I0C2

Figure

3(e).

Operation 'C4 ~C~ ~C~ 4C~ ~C~ 2.~ 2-~ 2.~ 2.~

~e 1 Sr Ti+~ O Ti+0 Ti+~ O Ti+~ O

.'. E w a = l S r + l T i + l 0 = 4 Figure 3 (d).


Operation 1C2' 2C2' ~C2' 4Cz' ~Cz' 6C~' ~C~' ~C~' "C~' o~ 1 Sr 2-~ T i + ~ O 2. ~ O 2.~ T i + ~ O 2.41- O 2.~ T i + ~ O 2.0 2"~ T i + 0 2- 0

(Oh factor group) E 8C3 6C2 6C4 3C~' i 6S4 8S~ 3ah 6ae

5 2 3 3 5 5 3 2 5 3

15 0 -3 3 -5 -15 - 3 0 5 3

Calculation of the n u m b e r of modes in each of the species n(~) = n u m b e r of modes in species g = order of the group g~ = n u m b e r of elements in each species x~(~) = t h e character for the species i and irreducible representation F ~ Xp~ = c h a r a c t e r of the irreducible representation, given above

.'. ~ 170

=Sr+Ti-/-3 0=5
Volume 25, Number 2, 1971

sc~~%z
4C 2 %

(b)

4
I Ici 4 I

4S~
['IS~

2S~
II,

(c)
Planes ~ 7 ~

(e)

"~ ~

~...-le~%~ ~0--~----~--~

/Ldniersec?ion of" Reflection

7-"
I ....:.:..-.

~'~

\ ~ 1

its

o6 (f)

oz

I I

(g)
x:::. "~1

!::1 (h)

"
J

~
J

'

,~ ~ - - - o ~ . - , - -

Fro. 3. (a) Unit cell of SrTiO3 showing 7C3 operations ; (b) unit cell of SiTrO3 showing C~ operations ; (c) unit cell of SrTiOa showing C4 operations ; (d) unit cell of SrTiOa showing C2' operations ; (e) unit cell of SrTiOa showing $4 operations ; (f) unit cell of SrTiO3 showing S~ operations ; (g) unit cell of SrTiO~ showing the aa operations ; (h) unit cell of SrTiO~ showing the o-a operations. E x a m p l e s of its u s e : (1) A l g s p e c i e s Oh E 8C3 6C~ 6C4 3C2' X,A'~= 1 1 1 1 1 xpi =15 0 --3 3 --5 gi = 1 8 6 6 3 g =48 i 1
-15 1

(4) A l l t h e o t h e r s p e c i e s of 0h g i v e z e r o i r r e d u c i b l e representations. 6S4 1


-3 6

8S6 3ah 1 ]
0 8 5 3

6ad 1
3 6

pcrystal = 4 F l , + F 2 , ~crystal __ pcrystal Facoustical 4 F F n o w Xvibratio n - - x -~ la T 2u - - t' l u pcrystal _ _ 9 ~ .

(5) S u m m a r i z e

vibration- or' l u-P ~' 2u.

2;xiA~'xPi" g; = 15 + 0 -- 18 + 18 -- 15 -- 15 -- 18 + 0 + 15 + 18 = O.

This checks our previous result. I t is n o w e a s y t o c o m p a r e t h e t w o m e t h o d s a n d see that the correlation method takes only minutes while t h i s m e t h o d i n v o l v e s h o u r s of w o r k .

". T h e r e are no l a t t i c e v i b r a t i o n s in A ~ species.


(2) F ~ s p e c i e s
Xi F l u =

E 3
1

8C3 0

6C~ --1

6C4 3C~' 1 --1

i --3

6S4 --1

8S6 1

3~,~ 6O'd 1 1

xp~ =15
g~ =

0
8

--3
6

3
6

--5
3

--15
1

--3
6

0
8

5
3

3
6

APPENDIX

IV

Correlation

Tables

~x~x~i .g~ = 4 5 + 0 + 1 8 + 1 8 + 1 5 + 4 5 + 1 8 + 0 + 1 5 + 1 8 g =48

=4.

Correlation tables are available in most books on spectroscopy1.11; however, we choose to show the d e r i v a t i o n of s e v e r a l t a b l e s . F o l l o w i n g t h e s e e x a m p l e s o n e c a n a l l e v i a t e t h e p r o b l e m of c h o o s i n g t h e c o r r e c t

". T h e r e a r e f o u r F ~ , i r r e d u c i b l e r e p r e s e n t a t i o n s . (3) F 2 , s p e c i e s
E

8C3 6C2
0 +1

6C4
--1

3C~'

6S4
1

8S6 3 ~ .
0 1

6~ d

correlation table when two or more possibilities exist, or, i n s o m e cases, w h e r e n o d i r e c t c o r r e l a t i o n is g i v e n in the published tables. T h e first e x a m p l e is t h e s i m p l e c o r r e l a t i o n of t h e point group C3, t o D3~. F i r s t , we write the point g r o u p C ~ as f o l l o w s .

xf~.=

--1

--3

--1

x,~ gl

=15 = 1

0 8

--3 6

3 6

--5 3

--15 1

--3 6

0 8

5 3

3 6

EXXp~.g, :45+0 -- 18 -- 1 8 + 1 5 + 4 5 -- 1 8 + 0 + 1 5 -- 18 = 1. g=48

.'. T h e r e is 1 F2~ i r r e d u c i b l e r e p r e s e n t a t i o n .

APPLIED SPECTROSCOPY

1'71

Car A~ A2 E

[ 1 1 2

2Ca (z) 1 1 --1

3try 1 -1 0

Point group D2a A1 A2 Bi B2 E

2S4 (z) $ 4 ~ C ~ '' 1 1 -1 --1 0 1 1 1 1 --2

2C~'

2ae

~'OW Car 1S a subgroup of Dab. This is easy to see for Da~ contains the same s y m m e t r y operators as Ca,, i.e., I, 2Ca(z), 3 ~ plus additional operations ah, 2Sa, and 3 ~ . To obtain which species of Caw correlate with those species of Da~, one need only compare the character of those operations common to both point groups Da~ and Ca,; which in this case are I, 2Ca(z), 3~. To do this, we simply write the partial character table of Dab and including only the operations common to both Ca,. and Da~ as follows. Operation I 1 1 1 1 2 2 2Ca (z) 1 1 1 1 --1 -- 1 3a~ 1 1"~ -- ~ J 1 0~

1 1 1 1 2

1 -1 1 -1 0

1 -1 -1 1 0

Now the operations of D4~ which are similar to D2d a r e two sets: (1) I, 2S4(z), C~, 2C2', 2ze and (2) I, 2S4(z), C2, 2C2", 2~,. These subgroups differ only in the presence of the CJ and zd in subgroup 1 and the replacement of these operations with C~" and c% in subgroup 2. Repeating the procedure previously discussed, the operations common to b o t h the point group Dth and D2a can be written as follows.
Species with same character in point 2ad group D2d
1 -1
-1

Dab species An' A~" A~' A~" E' E"

Caw Poini~ group species A~ A~ Ai E Subgroup 2 of D4h I


Alo

2S4(z)
1 -1
1

$42~C2 ',
1 1
1

2C2'
1 1
-1

A~u
A2o

1 1
1

A~ B~
A2 B2

A=u B~g B~,


B2o B2.

1 1 1
1 1

-1 -1 1
- 1 1

1 1 1
1 1

-1 1 1
- 1 --1

1 -1 1
1 --1

B~ A~
B2 A~

The species of each point group are compared, below, to find the correlation.
Operation I Point. group Da~ : species A~' Point group Cat. : species A 1 1 1 2Ca (z) 1 1 3a~ 1 1

Eo E~,

2 2

0 0

--2 --2

0 0

0 0

E E

Subgroup 2 of D4h I
Alo Alu
Ago A~ Blo Blu B2~

284(z)
1
--1 1 --1 --1

$42-~C2 2C2"
1
1 1 1 1

2av
1
-1 -1 1 1

Species with same character in point group D2e


Ai
B1 A2 B2 B2

Therefore, the correlation is Ca~A1 to

Da~Alt.

Also,

1 1
1 1 1

1
1 -1 -1 --1

Operation

1
1

1
- 1

1
1

--1
1

--1
- 1

A2
B~

I
Point group Da~: species A { ' Point group Ca,: species A~ 1 1

2C3(z)
1 1

3~r~
-1 -1

B=. E~ E~,

1 2 2
:

1 0 0

1 --2 -2

1 0 0

1 0 0

A1 E E

Summarizing The correlation is C~.A: to DahA1H. The other correlations found as above are summarized below.
Dan Car Da~

(1)
D4h

(2)
C~" ---~C~' D2d A1 B~ A2 B2 B2 A~ B1 A E E

C2' ~ C~' Deal Ax B~ A~ B~ BI Ai B~ A~ E E

Car A1 E E

Ai' Aa" A~'

A~ A2 A~.

A~" E' E"

The correlation between D.,a and DAb is a bit more complicated since D4a contains two different subgroups which are identical to D2e. I t is best to illustrate this case with the specific example, first the point group of D~d can be written as follows.
172.
Volume 25, Number 2, 1971

Alo Ai,, A~ o A~,, Blo Bi,, B2o B~, Eo E,

Therefore, to choose the correct correlation table one must consider the s y m m e t r y elements in the site group and which of these s y m m e t r y elements coincide

with in the factor group. This is exactly the problem one faces in selecting the proper correlation tables in the Ti02 example previously discussed. Here one must decide if the C~' element of the site D2e coincides with the C2' element of the factor group. Also, the ~d plane of the site group must coincide with the ere plane of the factor group, then one can choose the correlation tables marked C2'---~ C2'. However, if one finds the C2' element coincides with the C~" operation of the factor group and the ~ plane of site then coincides with the ~d plane of the factor group then one must choose the correlation tables where C2" ~ C2' as one does in the case of the titanium atom site in Ti02 and NH4I crystal. Tables relating the correct correlation to be used for each site are available by writing to the authors. These tables eliminate the necessity

of relating the site s y m m e t r y elements to the factor group symmetry, as described above. 1. D. F. Horn ig, J. Chem. Phys. 15, 1063 (1948). 2. H. Winston and R. S. Halford, J. Chem. Phys. 17, 607 (1949). 3. S. Bhagavantam and T. Venkatarayudu, Theory of Groups and Its Application to Physical Problems (Bangalore Press, Bangalore City, India, 1951), 2nd ed. 4. C. Kittel, Introduction to Solid State Physics (Wiley, New York, 1966), 3rd ed. 5. J. C. Slater, Quantum Theory of Molecules and Solids (McGraw-Hill, New York, 1963-1967), Vols. I-III. 6. J. Durig and D. J. Antion, J. Chem. Phys. 51, 3639 (1969). 7. International Tables for X-Ray Crystallography, edited by N. F. M. Henry and K. Lonsdale (T. Kynoch Press, Birmingham, England, 1965), 2nd ed., Vol. 1. 8. R. W. C. Wyckoff, Crystal Structures (Interscience, New York, 1963, 1964), Vols. I and II. 9. E. B. Wilson, Jr., J. C. Decius, and P. C. Cross, Molecular Vibrations (McGraw-Hill, New York, 1955). 10. D. M. Adams, Metal-Ligand and Related Vibrations (St. Martin's Press, New York, 1968). 11. R. K. Khanna and C. W. Reimann, (Correlation Method), Spectra-Physics Raman Tech. Bull., No. 3, 1970.

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APPLIED SPECTROSCOPY

173