Artigo Porto Normal Mode Determination in Crystals

SERGIO P O R T 0 COMMEMORATIVE ISSUE
Normal Mode Determination in Crystals

~~
D. L. Rousseau
Bell Telephone Laboratories, Murray Hill, New Jersey 07974, USA
R. P. Bauman
Department of Physics, University of Alabama in Birmingham, Birmingham, Alabama 35294, USA
S. P. S. Porto
Instituto de Fisica, University of Campinas, Campinas, Brasil
~~
The group theoretical methods by which the symmetries of normal modes in crystals may he determined are
outlined, and a series of tables are presented to facilitate rapid determination of the selection rules for vibrational
transitions. Emphasis is placed 3n the method of nuclear site group analysis in which the number of infrared and
Raman active modes of each symmetry may he obtained without detailed analysis of the symmetry elements in
the crystallographicunit cell or the construction of correlation tables. By using the tables presented here for most
cases identification of the crystallographic space group is sufficient information to allow determination of the
vibrational mode selection rules by inspection. Several examples are included in which crystals are analyzed by
each of the methods.
INTRODUCTION
The current interest in phonon spectroscopy, which has

been stimulated by the development of the laser for
Raman scattering and the steady advance of interferometric techniques in the far-IR, has made the rapid
determination of selection rules for vibrational transitions most important. However, owing to the wide
diversity of molecular and ionic crystals which may be
studied, a variety of techniques are necessary to treat
each problem appropriately. Analysis of the internal
motions of a crystal relies heavily upon the symmetry
properties of the crystal, which are best treated on the
basis of group theory. Although the theory is not quite as
simple as for molecules, the methods are quite similar.
The determination of the number of vibrational modes,
their symmetries, and hence the selection rules for I R
absorption or Raman scattering, may be carried out in
the same general manner as for free molecules,''2 bearing in mind a few differences to be discussed and the
absence of rotational and translational freedom for the
unit cell. The purpose of this paper is to present the basic
group theoretical methods which may be employed to
determine crystal selection rules, to illustrate the
methods with examples, and to present a set of tables
organized to facilitate rapid vibrational selection rule
determination. It must be emphasized that the paper is
intended to enable the researcher to quickly and conveniently determine the selection rules from a minimal
amount of crystallographic data. Keeping this in mind
proofs and justifications of the techniques described
have been omitted so that the methodology would not
become lost. Ample references have been included so
that the interested reader may, if he wishes, consult the
original works and study the mathematical foundations
of the methods.
There are several methods by which the unit cell may

be analyzed and the selection rules determined. Some of
these methods consider only k = 0 p h ~ n o n s ~(i.e.
. ~ near
.~
the Brillouin zone center) and others consider points
throughout the Brillouin zone.6 Generally the first order
phonon spectrum (near k = O), exhibits the greatest
intensity and is the object of the vast majority of
investigations. For this reason only k = 0 techniques will
be discussed in this paper. There are three techniques of
selection rule determination at the zone center. First is
the factor group analysis m e t h ~ d ,developed
~
by
Bhagavantum and Venkatarayudu, in which the symmetry properties of the crystal are determined by studying the effect of each symmetry operation in the factor
group on each type of atom in the unit cell.
The second method is one which we wish to label as
molecular site group analysis as presented by Halford4
and H ~ r n i gIn
. ~this technique the symmetry properties
are determined first for the unit of interest (i.e. a molecule or an ionic grouping in the unit cell) as an isolated
species. These results are then analyzed in terms of the
site symmetry and finally in terms of the factor group
symmetry. Winston and Halford7 demonstrated that this
method is equivalent to the factor group analysis
method. Detailed discussions of this technique have
been made recently by Fateley etal.' and by Ferraro and
Ziomek.'
A third technique was developed by Mathieu to treat
molecules.'" In this paper this last method, which we
term nuclear site group analysis, is extended to crystals
and is presented in conjunction with a set of tables to
greatly ease the burden of selection rule determination.
This method is simply a generalization of the molecular
site group analysis in that a site symmetry analysis is
carried out on every atom in the unit
By determining the site symmetry of each atom in this way a set of
tables may be constructed to allow symmetry and selection rule determination without the construction of a
CCC-0377-0486/81/0010-0253 $19.00
@ Heyden & Son Ltd, 1981
JOURNAL OF RAMAN SPECTROSCOPY, VOL. 10, 1981 253
D. L. ROUSSEAU, R. P. BAUMAN AND S. P. S. PORT0
correlation diagram." Such a set of tables (Tables B) are

included here.
Space groups, point groups and factor groups

The symmetry of an infinite crystal in its equilibrium
configuration may be described by a space group. This is
a group of symmetry operations, which obey the
mathematical criteria for a group, and which, through
their application on the crystal, either leave each atom
unchanged or carry it into an identical atom. An infinite
set of translational symmetry operations in addition to
point group symmetry operations constitute a space
group. (A point group consists of a set of symmetry
elements all of which pass through a single point.)
Rather than using the infinite space group to determine
the symmetry properties of a crystal, it has been found to
be an excellent spectroscopic approximation to consider
only a single unit cell of the crystal and treat the infinite
set of translations between unit cells as identity operations. The atoms within a unit cell are related by the
familiar point group symmetry operations in addition to
screw axes and glide planes. (A screw axis symmetry
operation is a rotation followed by a translation along
the axial direction. A glide plane operation is a reflection
across the plane followed by a translation along the
plane.) By thus separating out the translations, a finite
group remains, which is a factor group of the space group
and which describes the symmetry of a unit cell. It has
been termed a unit cell group or a factor group and is
isomorphous with one of the 32 crystallographic point
groups. The crystal class, as defined originally by the
analysis of the external symmetries of the crystal,
determines which of the 32 point groups is applicable to
a particular crystal.
The factor groups differ, however, from the point
groups in several important ways.
1. There need be n o point within the unit cell that is left
invariant by all the symmetry operations, and therefore it is not necessary that rotational axes and
symmetry planes meet at a common point.
2. A point is considered to be invariant if it is either left
in place by a particular symmetry operation or is
carried over to a position, in an adjacent unit cell,
which it could have reached by a simple translation of
one lattice unit. That is, if it goes to a corresponding
point in another unit cell, or does not move, the point
is called invariant; but if it goes to another position
within the same unit cell, or to a position in an
adjacent cell corresponding to such other position in
the original cell, it is not considered to be invariant
under the operation in question.
3. As pointed out previously, some of the symmetry
operations will include translations by fractions of a
unit cell length (screw axes and glide planes). These
are taken as equivalent to, that is they map into the
same class as, the operations without the translational components. In particular, screw axes may
be substituted for, or mixed with, pure rotational
axes, and glide planes are similarly taken as
equivalent to mirror planes.
4. There may be more than one set of operations falling
within the same class. For example, there may be
254 JOURNAL
OF RAMAN SPECTROSCOPY, VOL. 10, 1981
more than one center of symmetry, or where one C2

axis is present in the point group, there may be
several (e.g. four) C2 axes in the unit cell group, all
equivalent by symmetry, or there may be several C,
axes plus several two-fold screw axes, all these
operations mapping onto the simple C2axis of the
point group.
It is through the multiplicity of possibilities described
above that the 32 point groups give rise to 230 unit cell
groups. These factor groups are normally labelled either
by the Schoenfliess symbol in which the point group of
the crystal class (e.g. C2") is given a numerical right
superscript to designate the factor group (e.g. C;,); or
they are labelled by the Hermann-Mauguin symbols in
which the crystal class symbol (e.g. Pmm2) is modified to
indicate explicitly the substitution of a screw axis or a
glide plane (e.g. Pmc2,). A detailed description of the
labelling systems may be found in Vol. I of The International Tables For X-ray Crystallography.12Spectroscopists generally use the Schoenfliess symbols, while
crystallographers find the Hermann-Mauguin symbols
more convenient. Both symbols are used in the Tables
presented in this paper.
Site symmetry
Within the unit cell there are sets of points in which each
member of the set has an identical environment. These
points are designated as sites and the symmetry operations associated with one of these points define a group
(site group) which is a sub-group of the factor group and
is isomorphous with one of the 32 point groups permitted in crystal structures. Each member of the set shows
the complete symmetry of the appropriate site group for
that set. All the points within a set may be generated by
applying the operations of the factor group to one of the
points. The number of equivalent points, n, in a set is
equal to the order of the factor group, H, divided by the
order of the site group, h, i.e. n = H/h.
For example, in
the factor group D3d,there are 12 equivalent sites in a
set having C1symmetry ( n = 12/1), and 3 points in a set
with C2,,symmetry ( n = 12/4). From symmetry considerations the position of a point of given site symmetry
may be precisely fixed within the unit cell, or in cases of
the C,,,, C,,, and C, site groups, it may have from one to
three degrees of freedom since in these groups the sites
may lie anywhere along an axis, along a plane, or within
the volume of the unit cell. Therefore in unit cells which
contain these site groups of indeterminate position, an
infinite number of sets of such sites may exist within the
cell. For example in a unit cell belonging to the C:,
factor group there are four sets of C4,,sites each of which
contains only one equivalent point, two sets of C2h sites
with two equivalent points within each set, an infinite
number of sets of each C2and C, sites each of which has
four equivalent points, and an infinite number of sets
of C1 site symmetry with eight points per set. These
'special' positions are those the atoms may occupy when
distributed in the unit cell. The symmetry of the sites
then defines the symmetry of the local environment of
the atom occupying the site, and since it is very useful to
have at hand when determining selection rules, the
symmetry of all the sites of each factor group have been
tabulated in Tables A.
NORMAL MODE DETERMINATION IN CRYSTALS
SYMMETRIES AND SELECTION RULES OF

VIBRATIONAL MODES
Factor group analysis

The determination of the selection rules by direct use of
the factor group is a method analogous to the standard
technique for free molecules as long as the differences
between the point group and the factor group are kept in
mind. Symmetry analysis is made by applying all of the
symmetry operations of the factor group to each atom in
the unit cell, and reducing the representation thereby
obtained in order to determine the number of normal
modes belonging to each irreducible representation.
Consider a unit cell containing N atoms. Under a
certain factor group symmetry operation, R, there will
be some number of atoms U ( R )that are left invariant
(under the definition previously given). Each such atom
will contribute xT(R)to the trace in the ith class of the
reducible representation of the vibrational displacement
matrix. xT(R)is the trace under the operation R for a
vector displacement, and for Cartesian coordinates may
be given by
XT(R)= *1+2 cos &
(1)
the plus sign corresponding to a proper rotation (not
involving a reflection) and the minus sign arising for an
improper rotation (i.e. an inversion, reflection or rotation-reflection). The angle & is the angle of rotation for
the symmetry operation, R. Therefore the total contribution from all the atoms to a reducible representation
(I')of each symmetry operation R is determined by x ( R )
where
x ( R )= U(R)xT(R)
(2)
For a point group of m classes, one now has m numbers
x ( R ) . These are the characters of the reducible
representation of the motions of the nuclei of the unit
cell under consideration. This representation may be
reduced by the standard formula
or since within each class k, the x j ( R )are the same, Eqn

(3a) may be written as
In Eqns (3a) and (3b), nj is the number of times the

irreducible representation of symmetry species rj
appears in the reducible representation and is therefore
the number of lattice modes of symmetry rj;H is the
order of the point group; x j ( R )is the character of the
irreducible representation, Ti;X ( & ) and xi(&) are the
characters of the reducible and irreducible representations, respectively, of the kth class of the point group
containing g k elements (symmetry operations).
The selection rules for modes having the symmetry of
the various rj'sare determined by the character tables of
the point groups, so that when the number of modes, nj,
belonging to each rj has been found, the number of
spectroscopically active modes is known. In this manner
the correct number of lattice modes may be determined,
within the Born-von Karman approximation, and

excellent agreement with experimental observations are
obtained. In determining the values of U ( R )there are
two features of the unit cell which may give rise to
ambiguities.
It will be apparent that the symmetry operations that
include translations by fractional lengths of the unit
cell, i.e. the screw axes and glide planes, cannot leave
any point in the primitive unit cell invariant. Special
consideration must be given, however, to the nonprimitive centered structures. A screw or glide
operation will move a point to another point within
the same centered unit cell, or to a non-corresponding
point within an adjacent cell. However, to find the
number of distinct lattice modes we must choose as
our unit cell the primitive cell. For the purposes of
screw and glide operations, it is therefore necessary
to identify a priori which points within the centered
unit cell correspond to identical points within
different primitive cells, e.g. a corner and a center
point. The interchange of such points, then, cor.
responds to invariance when determining U ( R ) The
numbers U ( R )will be two or four times larger for the
centered unit cell than for the primitive cell simply
because the larger cell contains more atoms.
In determining the values of U ( R )for a given class it
is usually sufficient to consider the operations of a
given class together. However, in some instances the
nuclei are invariant to only one member of a class at a
time. In other words, one symmetry operation may
leave a certain nucleus invariant and interchange the
remaining equivalent nuclei in the set. Another
member of the same class will leave a different
nucleus of the set invariant and interchange the
remaining members of the set. If this is the case, in
evaluating U ( R ) the total number of equivalent
nuclei under all of the operations in the class should
be divided by the number of operations in the class,
or else a notation made as a reminder not to multiply
by the number of operations in the class (gk) when
applying Eqn (3b) to reduce the representation.
A more detailed Dicture of the svmmetrv modes of
the crystal may be obtained by independently considering each set of equivalent, and of course identical,
nuclei within the unit cell. The same procedure as outlined above is carried out for each of these smaller
sets of numbers U'(R). In this way one arrives at
sets of irreducible representations corresponding to
each set of nuclei. This can greatly facilitate the detailed writing of symmetry coordinates and also the
qualitative determination of the type of symmetry
modes that are appropriate to each irreducible
representation.
When there are distinguishable groupings within the
unit cell, which may be molecular (e.g. benzene, H2 or
Ss) or ionicspecies (e.g. Cog- or NO;), it is often helpful
to calculate separately the internal vibrational modes of
these groups and the external modes (often referred to
by others in the literature as the lattice modes) in which
the molecular group moves as a unit. The molecular
mode frequencies are generally higher than the external
lattice mode frequencies, and agree well, when
comparisons are possible, with frequencies observed in
gaseous or liquid samples. The external lattice modes
appear solely as a consequence of the crystalline structure. The separation of internal molecular and external
lattice modes may be easily performed.
The external lattice modes are of two types, which
may be described as translations and rotations of the
molecular groupings. (The translations exist even for
single atoms or icins;the rotations apply only for diatomic
or polyatomic groupings.) The acoustic lattice modes
may be considered as translatory modes of the unit cell
as a whole.
The numbers of internal and external modes may be
calculated by finding the characters of the representations for the several types of motions. For all possible
motions, the character is U ( R ) x T ( R ) ,as given previously. The representation of the acoustic modes has
the character xT(R).Translatory lattice modes (including the three degrees of freedom corresponding to
acoustic modes) give rise to the character [ UM(R)+
UA(R)]XT(R),
in which UM(R) is the number of polyatomic molecular units left in place (though possibly
rotated) by the operation R and U A ( R )is the number of
monatomic particles, not included in any of the molecular groupings, left in place by the operation R . Similarly,
the character of the representation of rotatory lattice
modes is UMxrot(R),where XrOt(R)is the character,
under the symmetry operation R , of a general r ~ t a t i o n , ~
and may be written as
Xrot(R)= * X T ( R )
= f ( *1+ 2
cos f$)
= 1* 2
cos f$
(4)
Here we adopt the usual convention in which the upper

sign is for a symmetry operation that is a proper rotation
and the lower sign is for a symmetry operation that is an
improper rotation (involving a reflection).
The total number of external lattice modes, including
the acoustic modes, is therefore
[LTM(R)-kUA(R)IXT(R)+UM(R)Xrot(R)
(5)
and the number of internal molecular modes is found by
subtracting this number of external modes from the total
number of modes. That is, the character of the representation for the internal molecular modes is
Nuclear site group analysis

The methods of site analysis provide a completely
different procedure for obtaining similar symmetry
information. Coinsider a factor group, G, of order H. As
stated previously a site group, g, which must be a subgroup of G will have order h and n equivalent points of g
site symmetry where n = H / h . Each class of sub-group g
will map onto one or more of the irreducible representations of the group G. Therefore motions of nuclei
determined for their site positions, may be correlated
into the factor to obtain the complete description of all
the nuclei in the unit cell.
The number of lattice modes arising from each
equivalent set of nuclei, their symmetries, and their
selection rules may be obtained by the following procedure. Assume the ith set of nuclei rests on sites of point
symmetry g, within a unit cell of symmetry corresponding to the point group G. In the sub-group g, one, two or
three of the irreducible respresentations will correspond
256 JOURNAL OF RAMAN SPECTROSCOPY, VOL. 10, 1981
to the behavior of the three components of a vector.

These are simply the irreducible representations of g,
said to have allowed I R activity. The irreducible
representations of G onto which the IR active irreducible representations of g, map, give the symmetries
(under G ) of the lattice modes arising from the ith set of
nuclei, occupying the sites gi.
There are certain generalizations that simplify this
mapping procedure. For example, sites of symmetry C1
give rise to three modes belonging to each nondegenerate symmetry species of the point group of the
unit cell, to six modes belonging to each doubly
degenerate species, and to nine modes belonging to each
triply degenerate species. When two vector components
transform under the same symmetry species of g,, the
number of modes for the unit cell is similarly doubled. A
convenient check of the mapping operation is given by
the condition that for each site symmetry, g,, the number
of lattice modes (number of non-degenerate plus twice
number of doubly degenerate plus three times number
of triply degenerate frequencies) is three times the
number of nuclei occupying those sites (i.e. 3N degrees
of freedom). In the mapping process it is necessary to
distinguish between irreducible representations of
dimension two and the separably degenerate, or
reducible, representations of dimension two; the latter
are not to be considered as degenerate in the restricted
sense of this paragraph.
The technique to use is the following: the space group
appropriate for the crystal under investigation must be
known as must be the number of nuclei of each type
within the unit cell. Then one must consult the tables
presented in this paper for that space group to determine
which site symmetries are compatible with it (Tables A).
Frequently the number of nuclei of a certain type within
the unit cell may be placed only on a single set of sites
compatible with the space group. If more than one set of
sites are possible for any set of nuclei then a more
detailed analysis of the crystal must be made to determine the symmetry. This may often be most easily
accomplished by comparing the X-ray crystallographic
data with the map of the unit cell given in Ref. 12.
Having established the site symmetry of each kind of
nucleus, only the mapping procedure remains, in which
irreducible representations of the three vector
components are mapped onto the irreducible representations of the factor group and the total number of lattice
vibrations is thereby determined. Tables of this
information (Tables B) are included in this paper and
will be discussed subsequently.
Molecular site group analysis

If distinguishable molecular or ionic groups exist in the
unit cell methods analogous to those discussed above
may be applied and the external motions of these
species may be readily determined. Consider a molecuIar grouping, M, which has symmetry described by the
point group G M and which is located in a unit cell
described by the point group G. The molecule M must
be centered on one of the lattice sites, which we may
describe as a site of symmetry gi,one of a set of n
equivalent sites in the unit cell. The group gi then must
be a sub-group of both G and GM. Exactly analogous
considerations of the groups giand G as for the nuclear

site group analysis case give the translational lattice
modes (including the acoustic modes) attributable to the
n equivalent molecules. (These data are presented in
Tables B.) By classifying the rotational degrees of
freedom in sub-group gi,and by then correlating this
information with the factor group G, the librational
lattice modes may be obtained in a similar fashion. (This
information for non-linear polyatomic molecules is
tabulated in Tables C.)
A more thorough analysis may be made, though
slightly more time consuming, in which all the motions of
the free molecule (or ion) are considered and the effects
on these motions of the site symmetry and the unit cell
symmetry are determined. An isolated molecule M of
symmetry G M may have q vibrational degrees of
freedom in addition to three rotational and three translational degrees of freedom. When the molecule is
placed on some site of symmetry gi of equal or lower
symmetry than GM, a correlation may be made between
the irreducible representations.of G M and those of gi. In
this way the vibrational, rotational and translational
degrees of freedom may be followed so to speak from its
isolated free molecule symmetry to its restricted site
symmetry. Since the symmetry of the site is always equal
to or lower than that of the free molecule (gi is a
sub-group of GM) vibrational modes which had been
inactive to IR absorption or Raman scattering may
become active due to the lower symmetry. The irreducible representations of the site group are then correlated with those of the unit cell group to determine the
final number of lattice modes. A set of correlation tables
are included in this paper in Tables D. The effect of
going from the site group to the unit cell group is to cause
splittings of the free molecule frequencies. This splitting
is often referred to as correlation field splitting and
results from the interaction between the n molecules in
the unit cell.
Selection rule breakdown in Raman scattering

Generally, the group theoretically determined selection
rules hold very well. Occasionally, experimental
difficulty arises in both IR absorption and Raman scattering in which apparent violations occur due to
depolarization effects owing to anisotropy and optical
rotation in the crystal. When appropriate technique^'^
are applied, these problems may be overcome usually
and the predicted behavior observed. However there are
two situations, unique to Raman scattering, which can
exhibit selection rule breakdown. These are effects
caused by incident laser resonances with real electronic
transitions (resonance Raman scattering) and splitting
due to long-range electrostatic forces. In both of these
cases the first order phonon spectrum is modified. We do
not discuss the problem of multiple phonon scattering
in which k = 0 selection rules are no longer valid and
points throughout the entire Brillouin zone must be
considered.
It is usually assumed that the polarizability tensor for
phonons is symmetric, and this appears to be a very good
approximation when the exciting frequency for the
Raman spectrum is far from an electronic absorption
band. If proximity to an absorption band does produce
0Heyden & Son Ltd, 1981
asymmetry, the selection rules will be modified, by

addition of allowed transitions that were previously
forbidden. In particular, in listing the transformation
properties of the components of the polarizability
tensor, as in Tables E, entries appear of the form a X y .
These entries arise from the sum a x Y + a y xThe
.
which is assumed to be of zero
difference term, ax,,- ayx,
magnitude, will usually have different transformation
properties. Under conditions of resonance excitation
such modes may become allowed and therefore may
appear in the Raman spectrum.
The difference terms for off-diagonal tensor
components are not listed as such in Tables E although
they have precisely the transformation properties of
rotations. R, transforms as a X y
- a y x ,R, transforms as
ayz- a z y , and R, transforms as a,, -a,,.
The transformation properties of these rotations are explicitly
given in Tables E. In addition to thc observation of
asymmetric components in the Raman tensor other
selection rule breakdowns due to properties of the
resonant excited state have been r e p ~ r t e d . ' ~
When Raman active phonons are simultaneously IR
active they carry a polarization which results in a
frequency splitting between the transverse and longitudinal waves. This splittin is reflected by the Lydanne1E
Sachs-Teller relationship in which the static dielectric
constant so is related to the high-frequency dielectric
constant sm by
(7)
for a crystal in which there exists only one optical polar

phonon. This phenomenon has been well characterized
and has been found to give rise to three anomalies in the
Raman s p e c t r ~ m . ' ~
1. 'Extra' lines appear due to the removal of the transverse and longitudinal degeneracy.
2. In various orientations these lines are found to shift in
frequency. The frequency shifting results from the
variation in the strength of the coupling caused by the
short-range and the long-range forces in the crystal.
To predict this shifting properly it is necessary to
consider the magnitude bf these forces and to
consider carefully the geometrical arrangements and
thereby determine which kind of phonon (transverse
or longitudinal) is being observed.
3. The intensities vary as a function of orientation in a
manner not predictable by simple group theory. To
interpret the intensities properly, again it is necessary
to consider the magnitude of the crystal forces and
the geometrical arrangement. By drawing momentum conservation diagrams" one can easily predict
the frequency shifts and intensities such that the
spectra may be well understood. In the construction
of the diagrams it is necessary to know the macroscopic polarization associated with each phonon.
Loudon" has discussed this and gives a set of tables
of this information. In Tables E of this paper this
information is also included in the following way: the
polar phonons are those in which there is allowed IR
activity. This is designated by the polarization directions X , Y or Z. If the phonon is Raman active the
polarizability tensor components are written in the
correct order such that a one to one correspondence
I). L. ROUSSEAU, R. P. RAUMAN AND S. P. S. PORT0
may be made between the tensor component and the

associated polarization direction. For example,
consider Table 19E (C3,). An A 1 phonon is
polarized in the 2 direction. Therefore the tensor
components a,,, a y yand a z zare all polarized in the 2
direction. The polarization for an E phonon reads
( X , Y )and the two sets of degenerate Raman tensor
components associated with this read (xx-yy, xy),
and (yz, xz). Therefore, the x polarization is associated with aXx,
a y yand aYz(the first term within each
of the sets of parentheses). Similarly the a,? and ax=
phonons are polarized in the Y direction.
TABULAR PRESENTATION OF SYMMETRY

INFORMATION
Whichever calculational procedure is employed, the
information of direct interest is determined by the site
symmetry and the unit cell point group. Therefore, since
there are only 32 point groups that can describe the
symmetry of crystals, and only 230 finite space groups
for which the sites must be determined, it is possible to
present all of the necessary information in the moderate
number of tables, given below.
At the heading of each set of tables is given the
Schoenfliess notation of the point group (followed by the
Hermann-Mauguin symbol for Tables A). Tables A
present the finite space groups by number, with the
Schoenfliess and Hermann-Mauguin symbol of each,
followed by the total number of possible site symmetries
for that space group. The number of equivalent sites of
the given symmetry is given in parentheses immediately
after the point group symbol for the site symmetry, and
the letter, or letters (Wyckoff notation), identifying the
set or sets of sites of the same symmetry are given
preceding the point group symbol. For example, the
entry m(f+ e ) C ; (4), among the sites for the finite space
group D:d (P4b2), indicates that there may be four
equivalent nuclei occupying the sites designated f on
C, axes parallel to the z, or c, axis of the crystal, and that
there may be also (or instead) four equivalent nuclei
occupying the sites designated * e , also on C2 axes
parallel to the z axis. Although most site symmetries
define a set of points, and can therefore be occupied by
only one set of nuclei in predetermined positions, the C,
and C,, sites (Cl, C2, C3, C4and Cg, and C, = Ctu, C2,,
GU,
and Go)are not unique and thus can be
occupied by more than one set of nuclei. In other words
there exists an infinite number of possible sets of the Cg
infinity
sites discussed above. This is indicated by
symbol preceding the Wyckoff letter notation. In this
same unit cell group (Dzd) we find from the table the
entry ( b + a)S4(2)which indicates that there are only two
sets of S4 sites ( b and a ) each of which have two
equivalent points per set.
The number of equivalent sites in any set is given by
the order of the point group divided by the order of the
site symmetry sub-group for the primitive (symbol P )
and primitive rhombohedral (symbol R )lattices, but the
number is greater for the centered lattices. The sidecentered lattices (symbol A , B or C) have twice as many
points, the body-centered lattices (symbol I)have twice
as many points, and the face-centered lattices (symbol
F ) have four times as many points as the primitive lattice

structures. Also, the rhombohedral lattices may be
represented by a hexagonal unit cell, which will have
three times the volume and thus contain three times as
many points as the rhombohedral cell.
For many of the point groups there are nonequivalent symmetry elements of the same type and
therefore non-equivalent sites of the same symmetry. In
most of these point groups it is sufficient to indicate the
diagonal elements, and the site point groups derived
from them by primes, or to add superscripts giving the
axes lying in or parallel to the symmetry elements.
Where there is possible ambiguity of labeling, the
method of labeling is indicated below the table.
Tables B, for each point group, list each possible site
symmetry for the finite space groups corresponding to
that point group, and give the number of lattice modes,
of each symmetry, produced by a set of nuclei on such
sites. Tables C are a mapping, onto the unit cell point
group, of the site symmetry point group irreducible
representations that correspond to pure rotations.
Tables D are a set of correlation tables giving the
correlation map for all subgroups of each point group.
Tables E are a set of character tables of the point
groups, and also contains the character of a general
vector, XT defined in Cartesian coordinates. Symmetry
properties of translational vectors, and hence the electric dipole absorption selection rules, are given, along
with the symmetry properties of the rotations. The
acoustic modes belong to the representations which
contain the translation vectors. In the last column the
symmetry properties of the polarizability tensor
components are listed, which provide Raman scattering
selection rules.
Examples of calculations and use of the tables
In the examples which follow selection rules are determined for several crystals by one or more of the methods
discussed here. However, each crystal is analyzed by
nuclear site group analysis to demonstrate the facility of
this method and the convenience of the tables.
Sodium chloride is a well-known example of a cubic
face-centered structure containing four sodium ions and
four chloride ions per (non-primitive) unit cell. Since the
space group describing the crystal is Og, we find from
Table 32A that only Ohsites can accommodate two sets
of four equivalent points in each. The lattice modes can
now be read directly from Table 32B. Each set of nuclei
(sets a and b ) on sites of symmetry Oh give rise to one
triply degenerate mode of symmetry Flu.Thus NaCl has
two triply-degenerate lattice modes, both of symmetry
Flu.From Table 32E we find that these are IR active and
Raman inactive. One is an acoustic branch and the other
is an optical branch.
Another well-known face-centered cubic crystal is
diamond in which there are 8 carbon atoms in the 0;
unit cell. From Table 32A we find that these 8 equivalent
carbon atoms must lie on Td sites (on either set a or b).
From Table 32B a set of Td sites gives rise to two lattice
modes, one Flu and one F2g mode. The Flu is an
acoustic mode and the F2g is a Raman active optical
mode with off -diagonal non-zero tensor components.
Barium titanate, BaTi03, is also cubic ( 0 ; )in its
high-temperature phase, but changes to tetragonal (Citi)

Cb"
(0)
(b)
Figure 1. Unit cellsfor cubic (a) and tetragonal (b) barium titanate.
In the cubic phase the Ba2+ ions are at the cube corners, the 0'ions are at the face centers and the Ti4+ ions are at the body
centers. In the tetragonal phase the vectors represent the relative
directions that the atoms are displaced with respect to the cubic
phase. Adapted from Ref. 21.
at about 120 "C. These two structures, each containing

one formula unit per primitive cell, are illustrated in Fig.
1. It should be noted that the three oxygen atoms in the
unit cell are equivalent in the cubic phase; but in the
tetragonal phase the atom which lies along the unique
axis is distinguishable from the other two. We may
readily determine the symmetries of the lattice modes
for these two structures by the method of nuclear site
analysis (i.e. direct use of the tables).
For the cubic phase it may be readily determined by
consulting Table 32A that the barium and the titanium
atoms (one of each per unit cell) must occupy oh sites
and the 3 oxygen atoms must lie on D 4 h sites. From
Table 32B each nucleus on an O h site will contribute an
Flusymmetry mode and the three oxygen atoms will
contribute 2FlU+ F2u,giving a total of 4FlU+ F2u.The
acoustic mode is Fluas indicated in Table 32E, so the
vibrational modes have the symmetry species 3F1, +
F2u,of which the Flumodes are IR active and the FZu
mode is silent.
To determine the symmetry of the lattice modes of
the tetragonal phase (Ci"),it is necessary first to consult
Table 13A, in which it is found that only C4usites will
accommodate a single atomic species within the unit cell.
These sites are labelled a and b but we must remember
that there are an infinite number of C4usites within the
unit cell. Therefore the Ba, the Ti and the unique oxygen
all must occupy C4usites. The remaining two oxygens
must lie on C2, sites. Consulting Table 13B the lattice
modes from the Ba, Ti and unique oxygen are 3A + 3E.
Those from the remaining oxygens are A1 + B 1 + 2 E
giving a total of.4A + B1+ 5E. Table 13E shows that the
acoustic modes are A l + E and, therefore, there are 3A1
optical modes which are simultaneously IR and Raman
active, one B1 mode which is Raman active, and 4 E
modes which are also IR and Raman active. The IR
active modes split into transverse and longitudinal
waves. This will have no influence on the IR absorption
spectrum since only transverse phonons can interact
with the IR radiation. However, Raman scattering may
be observed from both transverse and longitudinal
waves and therefore twice the number of A l and E
modes predicted by group theory may be found in the
experiment.
A!.
t!.
t i
Figure 2. Symmetry operations of the cubic phase, 0:'of barium

titanate. This figure was adapted from Ref. 20 and uses the
standard notation for the various symmetry
It is also illustrative to determine the selection rules

for the cubic phase of BaTi03 by factor group analysis.
The symmetry operations'' for 0 ; are drawn in Fig. 2.
(These operations should be compared to the unit cell in
Fig. l(a).) The first step in the analysis is to determine the
value of U ( R ) for the barium, titanium and oxygen
atoms. The first two lines in Table 1, giving Us,(R) and
UTi(R),are straightforward. Each Ba atom is on a site of
o
h symmetry and is therefore invariant to precisely the
symmetry operations listed, and similarly for the Ti
atoms. Note, however, that the symmetry elements are
not necessarily the identical ones for Ti as for Ba. For
example, the C4 axes passing through Ti atoms do not
pass through Ba atoms and vice versa.
Table 1. Factor group analysis of BaTiO, in its cubic phase

Oh :
Us. :
U T i:
Uo:
UBaTiOa:
XT:
E 6C4 3 C i 8C3 6Cz

1
1
3
5
1
1
1
0
2
0 -
1
1
1
3
1
i 6S4 3uh 8Ss 6 r d

1
1
1
1
1
1
1
1
1
1
3
1
3
0
1
5
3
5
2
3
-3-1
1
0
1
1
1
3
5
3
1
1
1
3
1 -
1 - 1
0 - 1
-3-1
1 - 3
0 - 1
-9-1
The method of counting invariant oxygen atoms is less

obvious. There are three oxygen atoms per unit cell, so
three are invariant under the identity operation E.Also,
each is on a center of symmetry, each is on an intersection of three mutually perpendicular planes of symmetry (perpendicular to the unit cell edges), and each is
on an intersection of three mutually perpendicular CZ
axes parallel to the unit cell edges (of which only one is
actually also a C4axis). There are, under Oh symmetry,
necessarily three mutually perpendicular C4 axes (with
operations C4 and C:). Each oxygen atom ( D 4 h symmetry) is on only one C4 axis, and each C, axis leaves
only one of the three oxygen atoms invariant. This
applies as well to the three distinct S4 axes. Similarly,
there are necessarily six Cz axes, which pass diagonally
through the facles of the unit cell (and an equivalent set
passes through the center parallel to the faces), but each
oxygen atom is on two and only two of these six axes.
Furthermore, each of these Cz operations leaves only
one oxygen atom invariant, so U 0 ( 6 C z ) = l . The
diagonal planes of symmetry, 6 u d , similarly leave one
oxygen atom invariant. No oxygen atoms are on C3or S6
axes.
We next obtain the representations of the Ba, Ti and
0 motions b y multiplying the U ( R ) values by XT
obtained from Table 32E. Reduction of the representation for Ba and Ti motions is trivial; the representation
is clearly the irreducible representation Flu. The
representation of the oxygen motions is reducible to the
sum of irreducible representations, 2F1,+F2,.
Calcium tungstate (CaW04) contains four formula
units per body centered unit cell of space group
C,",(141/a). The modes for this rather complicated unit
cell may be readily found by consulting Table 11A. Since
there are four Ca atoms, four W atoms, and sixteen
identical oxygen atoms it is immediately seen by inspection of Table I1A that the calcium and the tungsten
atoms each must occupy S4 sites, and the sixteen oxygen
atoms must be on C1sites. From Table 11B the vibrational modes of the crystal are then 3A,+ 3A,+ 38,+
3B,+ 3E,+ 3E, for contributions from the oxygen
atoms and 2A,+ 2B,+ 2E,+ 2E, for the contributions
both from the calcium and tungsten atoms. The total
number of optical branches are 3A,+ 4A,+ 5 B, +
3B,+ 5E, + 4, while the acoustic branches are A, +
E,.We also find from Table 11E that the A,,B, and E,
modes are Raman active and the A, and E, modes are
IR active.
More information about the details of these vibrational modes may be obtained from the tables. First the
tungstate ion may be treated independently. In other
words consider a unit cell composed of two particles in
each formula unit-a calcium ion and a tungstate ion.
Each must occupy S4sites, and from Table 11B this gives
2A,,
t 2B, + 2Eg+ 2E, modes. A, + I:, are acoustical
modes 50 there remain A, -I-2B,+ 2E, + E,, modes
which are optical modes of translational character. By
consulting Table 11C we may also assign A, + B, + E, +
E, as librationill modes resulting from oscillations of the
tungstate ion. No librational modes may be found of
course from the Ca ion since it has no rotational degrees
of freedom. It should be pointed out that since E, and E,
modes arise from both translational and librational
motions, the normal coordinate describing these degrees
of freedom will be a combination of those symmetry
coordinates describing the librational and translational

motions and may not therefore be designated as pure
librational or pure translational modes. The total
number of 'external' motions of C a W0 4 are thus A, +
A, + 2B,+ B, + 3E,+ 2E,. By comparing with the
previous result for the total number of modes, the
'internal' motions of the tungstate ion are 2A,+ 3A,+
2B,+2B,+2Eg+2E,.
A more thorough analysis of these internal motions
may be obtained if the method of molecular site group
analysis is used. The isolated tungstate ion W0;- has T d
symmetry. By standard techniques* the vibrational
motions of this ion may be designated by the following:
A I ( Y I )E(vz),
,
Fl (rotation), 3F2 (translation, v3, v4).
These representations of T d specify the motions of the
W0:- ion, and the designations in parenthesis after
each representation are the standard Herzberg notations. 1 It is now most convenient to construct a correlation table by consulting Table D. In Fig. 3 each of the
T d representations are listed for the tungstate ion. Since
the ion occupies an S4 site, the effect of the lowering of
the symmetry is determined by forming the correlation
between the Td and the S4 representations. The contribution of the calcium ion, also on an S4 site, is only of a
translational nature. By then correlating the site symmetry representations to those of the unit cell, the effect
of having the several ions within the unit cell interacting
with each other is taken into account. To determine the
nature of each lattice mode it is now necessary to
consider its origin. The 3A, and the 3B, modes each
may be divided into a librational lattice mode and a
mode derived from each V I and VZ. The 5B, and the
5A, modes each contain two translational lattice modes
and modes derived from VZ, v 3 and v4. The 5E, and
the 5E, modes each result from two translational
modes, one librational mode, and v 3 and v4. It should be
noted that an A, translational mode and an E , translational mode form the acoustic branches of the crystal.
Of the internal modes, the mode v1 should appear only
in the Raman effect and as a single line. In the v z region
there should appear two lines in the Raman spectrum
(A,+ B,)and one in IR absorption (A,).
There should
be two lines for both v 3 and v4 in both the Raman
spectrum (B,+E,) and in the IR spectrum (Atd+EL,).
The magnitude of the splitting between any pair of these
modes is determined by the forces in the crystal and may
Ionic
species
Free
ion
sym.
Site
syrn.
Ca"
s
4
(trans,
A /
" 3 , @4)3F2
Unit
cell Vibrational
sym.
modes
c
4
,
f , , - 5 f o ( v 3 ,v4, trans, lib, acoustic)
Figure 3. Correlation table f o r CaW04. The translational (trans)

a n d rotational (rot) degrees of freedom of the free molecule
become translational (trans) and librational (lib) lattice modes i n
the crystal.
+=
I
(b)
(a)
Figure 4. (a) Body-centered unit cell (non-primitive) of calcium

tungstate with space group cih. (b) Symmetry operations for
Cih. This is from Ref. 12 and used the standard notation for
symmetry operations.
not be readily predicted. In many instances such splitting

is very small and therefore may not be observed.
Since Ca W 04 has a body-centered crystal structure it
also serves as an illustrative example to solve by the
method of factor group analysis. Preliminary consideration of the crystal with the tables greatly facilitates the
process, however. Remembering that we previously
determined that oxygen atoms are on C1 sites and the
calcium and tungsten atoms are on S4 sites, we may
immediately state which symmetry operations will
interchange the atoms in the unit cell and may therefore
exclude them from our consideration. (Any symmetry
operation not included in that group of operations
defined by the site symmetry will make a zero contribution to the number of unshifted atoms U ( R ) . )
The oxygen atoms will then only make a contribution
to U ( R )under the identity operation, while the Ca and
W atoms of symmetry S4 will have contributions under
E, C2,S: and S4.The values of U ( R )for the oxygens are
trivial, and are listed in Table 2. To determine the values
for the Ca and W atoms it becomes necessary to consider
the unit cell and the symmetry operations depicted in
Fig. 4.The C2axis and the C2 screw axis both map into
the same C2class in the C4,, point group. Consideration
of either will give the correct result. However, if the C,
screw axis is used it is necessary to identify the corner
position as being identical to the center position and the
lower side positions as being identical to the upper side
positions in a primitive cell. Since equivalent C2 axes
Table 2. Factor group analysis of CaWO, (face-centered,
non -primitive unit cell)
c4h:
uca:
u w:
uo4:
UCaWOa :
XT:
E C
,
4
0
4
0
1 6 0
2
4
3
1
C:
C
:
0
0
0
0
+I
-1
-4
4 8 0
72
0
0
0
0
-8
12
S,
i
0
0
0
4
4
0
S:
-1
4
4
0
8
-1
-4
-4
0
0
0
-8
-8
4
4
0
0
-3
Uh
0
0
0
0
+1
UWXT
:
UCaWO&T:
UO&T
Tea= Tw= 2A, + 2Bg + 2Eg + 2Eu.
ro4= 6Ag + 6A, + 6 4 + 6B, + 6Eg+ 615,.

rcawo4
= 6Ag + 10A, + 10Bg+ 6B, + 10Eg + 1OE,.
rcawo4(primitive)= 3Ag+ 5A,
+ 5Bg+ 38,
+ 5Eg + 56,.
0
0
pass through all calcium and tungsten atoms, to determine the number of unshifted atoms under this operation, the counting may be done by considering all of the
C2axes in turn, observing only those atoms being on the
axes. Alternatively only a single C2 axis may be considered and its effect on all of the atoms in the unit cell
determined. By either technique all the tungsten and all
the calcium atoms in the unit cell remain in identity
positions under the C2 symmetry operation.
The S4 axes are coincident with the C,axes previously
discussed. The corresponding planes associated with the
S4 axes pass through the tungsten and the calcium atoms
lying on the axis under consideration. Again one has a
choice of considering each of the S4 axes in the unit cell
and only its effect on those atoms being on it, or only one
and its effect on all the atoms in the unit cell. If only one
axis is used it is again necessary to identify the equivalent
positions based on a primitive cell analysis. The remaining results in Table 2 are found by standard techniques.
Twice the correct number of lattice modes are found by
this method because the centered unit cell is doubly
primitive.
Naphthalene and diphenyl belong to ,a large class of
compounds which crystallize in the C 2 h space group
with two molecules per unit cell. The external lattice
modes of these crystals may be readily determined by
use of the tables. Since there are two molecules per unit
cell, by consulting Table 5A we find that each molecule
must occupy a Cisite. Therefore we may read off the
translational degrees of freedom from Table 5B ( 3 A , +
3B,) are the librational modes from 5 C ( 3 A , + 3 B , ) .
The acoustic modes are A , + 2B,. Thus the external
lattice modes are 3A, + 3B, + 2 A , + B , of which the A ,
and B , are Raman active and the A , and B , are IR
active.
CONCLUSION
In this paper three methods of selection rule determination of k = 0 phonons have been described. The
primary purpose of this presentation was to organize
these techniques in a unified manner and to illustrate
them in light of the tables which have been included. It is
appropriate at this time to discuss some of the advantages and disadvantages of each method.
The most complicated method and the one which
requires the most thorough understanding of the unit
cell is that of factor group analysis. To determine the
selection rules of the lattice modes in this way a map of
the unit cell must be available and careful consideration
must be made of the effect of each symmetry operation
on every nucleus in the unit cell. However, if symmetry
coordinates are to be written explicitly it is necessary to
select generating coordinates (for example, a generating
coordinate might be a Cartesian vector located on a
specific nucleus), and apply each of the operations of the
factor group on it to generate the symmetry coordinates
for each irreducible representation. The entire procedure also consists of various orthogonalization
methods to obtain meaningful symmetry coordinates. If
such a detailed analysis of the symmetry modes is
desired it is best to initiate the study by determining the
selection rules by the method of factor group analysis.
D. L. ROUSSEAU. R. P. BAUMAN AND S. P. S. PORT0
If selection rules are to be determined for a crystal

which has distinct molecular or ionic groupings the
method of molecular site group analysis should be used.
Information will then be obtained showing how each
isolated internal motion will be affected by placing it in
the unit cell. This is extremely important information to
have at hand when trying to interpret IR or Raman
spectra of such crystals.
All crystals may be analyzed readily by the method of
nuclear site group analysis by using the tables presented
in this paper. Furthermore, this method may be applied
to free molecules equally well by determining the sym-
metry of each nucleus (site symmetry) and then determining the irreducible representations by inspection
from Tables B for the point group of the molecule. This
method should be extremely useful for both molecules
and crystals due to its speed and simplicity. While it may
be desirable to use one of the other methods it is often
convenient to determine the selection rules by this
method first since it is less subject to ambiguities and
human error than are the other methods. In any event it
is an important and easy technique that all spectroscopists should have at hand when studying vibrational
motions.
REFERENCES
1. G. Herzberg, Molecular Spectra and Mo!ecular Structure: I1
Infra-Red and Raman Spectra of Polyatomic Molecules, D.
Van Nostrand Company, Inc., Princeton, N.J. (1945).
2. E. B, Wilson Jr, J. 5. Decuis and P. C.. Cross, Molecular
Vibrations, McGraw-Hill Book Company, Inc., New York
(1955)
3. S. Bhagavanturn and T. Venkatarayudu, Proc. lndian Acad.
Sci. Sect A 9.224 (1939); S . Bhagavantum, Proc. lndian Acad.
Sci. SecF. A13, 543 (1941); S. Bhagavantum and T. Venkatarayudu, Theory of Groups and Its Application to Physical
Problems, Audhra University, Waltair, India (1962).
4. R. S. Halford, J . Chem. Phys. 14, 8 (1946).
5. 5, F. Hornig, ,J. Chem. Phys. 16, 1063 (1948).
6. A. A. Maradudin and S. H. Vosko, Rev Mod. Phys. 40, 1
(19681; A. t. Warren, Rev. Mod. Phys. 40, 38 (1968); G.
Venkataraman and V. C. Sahni, Rev. Mod. Phys. 42, 409
(1970).
7. H. Winston and R. S. Halford, J. Chem. Phys. 17,607 (1949).
8. W. G. Fatelev, N. T. McDevitt and F. F. Bentley, Appl. Spectrosc. 25, 155 (1971); W. G. Fateley, F. R. Dollish, N. T.
Pi/lcDevitt a m F. F. Bentley, Infrared and Raman Selection
Rules for Mderular and Lattice Vibratiom : The Correlation
Method, 'j\lile~i-lrirerscience, New York (1972).
9. J. R. Ferraro #and J. S. Ziomek, Introductory Group Theory
and Its Application to Molecular Structure, Plenum Press,
New Yoik (1975i.
30. J.-P. Mathleu Spectres De Vibration et Symetrie, Herman et
cie, Paris ;1945),
11. D. M.Adams and D. C. Newton, J. Chem. SOC.A 1970,2822.

12. International Tables for X-ray Crystallography. Inter nat ion aI
Union of Crystallography, Kynock Press, Birmingham, UK
(1952).
13. J. E. Rosenthal and G. M. Murphy, Rev. Mod. Phys. 8, 317
(1936).
14. J. F. Scott and S. P. S. Porto, Phys. Rev. 161,903 (1967); S. P.
S. Porto, J. A. Giordmaine and T. C. Darnen, Phys. Rev. 147,
608 (1966).
15. P. F. Williams and S. P. S. Porto, Phys. Rev. B 8, 1782 (1973).
16. R. H. Lydanne, R. G. Sachs and E. Teller, Phys. Rev, 59, 673
(1941).
17. H. Poulet, Ann. Phys. Paris 10, 908 (1955).
18. C. A. Arguello, D. L. Rousseau and S. P. S. Porto, Phys. Rev.
181, 1351 (1969).
19. R. Loudon, Adv. Phys. 13,423 (1964).
20. lnternationale Tabellen m e Bestimmung von Kristallstruktunen I, p. 354. Gebruder Borntraeger, Berlin (1935).
21. C. Kittel. Introduction to Solid State Physics, p. 404. Wiley.
New York (1966).
22. H. Strunz, Mineralogische Tabellen, Akademische Verlagsgesellschaft, Leipzig (1957).
Received 29 August 1980

TABLES
-I___
Ordering within each set of tables

Table
Crystal syste:?'
Triclinic
Monociin:c
0rt ho r ho m h ic
Tetragonal
Rhombohedra1
(Trigonal;
Point Group symbo s

Srhoenfliess
Herrrann-Mauguin
c,
C,
CZ
4
5
cs
-1
2
m
2/m
c2h
VI
021
c2"
DZh ( v h )
222
mrn2 (2mm, mrn)
mmm(2lm 21m 2 f m )
c4
16
'7
C,
s6(@3#1
Table
Point Group symbols
no
Schoenfliess
Hermann-Mauquin
18
19
20
7
3
10
Crystal system
Hexagonal
21
22
23
24
25
26
27
0 3
c3v
DBd
c6
C3h(S3)
cfih
D6
C6"
D3h
D6h
32
3m
3m(32/m)
6
6i3irn)
61m
622(62)
6mm
6m >!
6/mrn(6/m 2 l m 2 f m )
Tables A. All sites for each of the 32 crystallographic point groups
2A
5A
(i)
Ci
Space
Group
Sites
c:
(Pi)
.[iCl(2)]
:C
(Bllb)
C2,(2/m)
space
Group
(h+g+f+etd+c+b+a)ci(l)
-CaC1(4
)I
Sites
D. L. ROUSSEAU, R. P. BAUMAN A N D S. P. S. P O R T 0
ALL SITES FOR EACH POINT GROUP
TABLES 7A-9A
8A
D2h (m) continued
Soace

TABLES 10A-15A

10A
S4 ( 4 )
Space
Group
s:
12A
(pi)
1jA
C4v(4mm)
continued
l4A
Ded(42m)
space
Group
Sites
Sites
-[hCl(4)]
-[ (g+f+e)C2(2)1 + (d+C+b+a)Sh(l)
D4 (422)
SDaCe

TABLES 15A-20A
15A D,,,(&/mmm)
-11
SDace
continued
,"
Space

21A
c~(6)
Space

32A
Oh(mjlll)
space
Group
Sites
Tables B. Irreducible representations that result from occupying each of the sites within each space group. These give the
translational lattice modes
1B
C.
Site
D2h
Representations
3A
Site
Representations
C1
3Ag + 3Au + 3B + 3BlU+
c:(c;)
28
Ci
Site
C;(C;t
Representations
Xu
3Ag +
c1
3%
3B
C2
Site
3A"
2A'
A"
'2h
Representatims
C1
3Ag + 3Au + 3Bg + 3B,
ci
>AU + 3Bu
cs
A,
A,
2B + 2B1,+
18
AU
2A
2B
AU
2B1
2B2
CiZ( axz )
2A
+ %+
B + 2Blu+
16
c y (YZ)
2A
Blg
2Blu+
Ci
3% + 3Blu+ 3B2,+
3B3,
A,
2BLg
2B2u+ 2B
B2,+
Blu + B
2g
2B2u+ 2B
Ag
B1g+ Blu+
C&(C~oxy+oxz)
B + Blu+ B + B2,+
1g
2g
Bju
B3,
B + Blu+ B
1g
2B3,
3s
B3,
+ Bju
3g
B2,+
2B2,+
k+
B2,+
CZh( c;+ow)
A+,
CZh( c
A,
2Blu+
B2u+ 2B3,
c;,(c;+oYz)
A,
2Blu+
2B2,+
D2h
BlU+ B2u+ B3U
p y
2B3,
B2u+ B3g+ B3,
2g
Blu+
a
3
Cz,($+ow+d")
Blu+
2B2,+
B2,+
2g
B%+ B3,
2g
2BjU
3g
2B
C ~ y ( C ~ + a x z + ~ z ) Ag
3B3,
2B3g+ 2BjU
2B + 2B2,+
2g
PA
A,
2g
2Blu+
18
2B3,
B3,
2BU
2BU
3B
3E
A+B+ZE
A+ E
Site
Representations
C1
3A
3B
3E
B+ E
2B
A + B + 2 E
Blu+ 2B2g
cy( ow)
3A
A,
1g
3Bx+
Site
C2
C,"(C,X)
D2
5B
Representations
3A'
3B + 3B2,+
18
118 Cllh
Representations
3Ag+ 3Au+ 3Bg+ 3Bu+ 3Eg+ 3EU
3Au+ 3Bu+ 3Eu
A,
+ B, +
2E + 2EU
A,
2B
Site
Representatisns
Cl
3A1 + 3A2 + 3B1 + 3U2
2A
CP
A1
2B2
A,
+ BU +
C:z(ocz)
2A1
+ B2
+ A u + E
C?(<')
2A1
CP Y
A1
A;,
A2
B1
2B1
2B1
B1 + 2B2
+ B2
2E,
2EU
AU+B + E
g
Bu
+Eu
CE,
Au + Eu
D. L. ROUSSEAU, R. P. BAUMAN AND S. P. S . PORT0

REPRESENTATIONS WHEN EACH SITE IN EACH SPACE GROUP OCCUPIED
TABLES 12B-196
12B
15B
D4
Site
Representations
D;(C:+ZC;)
C;y(C~+20V)
+ 3E
c~v(c~+20d)
C (C +o+a )
2v 2 h d
A
A
3A2 + 3Bl + /B2 + 6E
+ B1 + B2 + 4 E
dl
A1
2A2
+ B1
c;(C;)
A1
?A2
+ 2B1
D2(C;+2C2)
A2
B2 + 2E
Cjy(C;+ah+od)
D;(C>ZC;)
A2
B1 + 2E
Dzh(C;+'c2)
A1
A2
+ E
C;(C;)
C2
(C,)
c4
D4
13B
/A.
continued
site
Representstions
C1
D,,,
A2
2B2
B2
3E
2E
A2U+
AZU+
2EK+
Aau+
u+Bl
B2.5+ 2Eg+ 2EU
A2$
%u+ B1 K+
1.5
1.5
lg
1.s+
Blu+
A2u+
1.5
2E
2g
2EU
2Eu
BzU+ E
2EU
2Eu
Blg B
2.s
B>u+ 2Eu
A2u+
c4
54
U
+A
I
A2u+
U
+A
l
'4 h
1K
+
1.5
2.s
Dj,(C22C;)
CuV
site
2.5
Blu+
18
2Eu
lU
2E
AZu+
2E t 2EU
B + B + Z E t 2Eu
1.3
2.s
.s
2EU
2u
Representations
3A.
C1
A1
c2
+ 3B1 + 3B2 +
/A2
A:,
B1
B2
c4
ZA.,
AT
+ 2B1 + B2 + 3E
cz(od)
ZA.,
A,;
+ B1
c2yv(~.z)
B1
2BP
Azu+ Eg+ Eu
%g+
"
AI K
A2"+
Eu
4E
C:(ov)
D4
6E
E + EU
K
D i d (C;+2C;+oV)
AZu+
B,
DZd(C22C2+ad)
AZu+
4' h
A 2 U + EU
dK
1.s+ E.s +
3E
Eu
2E
Al + B2 + 2E
Cgv(o,)
c4
A1
c4 Y
A1
A2
2E
+ 3E
3A
14B D2d
Site
A + E
Representations
+ XP+ 3B1 +
/AA1
C1
c:(C;)
A1
42
c2 (c,)
A1
2%
cs
PA1
D2
+ 4E
+ B1+B2
B1
3B2 + 6 E
+ $ + B1 + 2B2 +
A2
+ B2 + 2 E
A1
17B
2B2fjE
S,
Site
Representations
C1
?A
'i
C2Y
'2d
+ 3AU+ 3Eg+ 3EU
3Eu
3Au+
B:, + 2 E
A
s4
3E
B1
B-
B2
Au+
+ Eu
2E
'6
A u + EU
4
18B D,
Representations
3A
U
3A
+I
3BIu+
?Apu+
2g
3AA2u+ 3B + 5BlU+
16
site
Representations
C1
>A1
c2
A1
3BZK + 3BZu+ 6Eg+ 6EU
3BZu+ 6EU
AZU+ B1.s+ Blu+
+ A:?$
uAl
A1$
C;(Cz)
) A ~ $ >Aul+
Bpg+ Elzu+ 4Eg+ 4Eu
+ 3%'
A1+
C2(C2)
cj(C;)
c:(oh)
7A
c:(av)
?Agl+
C2(od)
1.s+
A
u+l
2A
Alu+
2A
l e+
av)
2K
2A2u+
+
2.s
+
PA
2K
A2u+
A
u+l
A 2.s
2AZu+
A 2.s
1.s+
Blu+ 2B2&i 2BZU+ 3Eg+ 3EU
D3
+
1.3
2BIu+
1.s+
Blu+
>AAzu+ 2 8
u+AI
?A 1 KiA
u+l
C:h(C36h)
C2h(C7+
k3
2%u+
+ Blu+
4EU
2B1.s+ Blu+
B2.si-2BZu+ 3E
3Eu
B1.s+ 2Bul+
2B2$
2B
2K
19B C3"
site
Representations
C1
)A+
l
>A2+
cs
2A1+
A2+
B2u+ /Eg+ 3EU
A
u+l-
PAzu+
Blu+ 2BPU+ Xu
u+Al
2A2u+
7Bul+
c3
C i h (C;+O,)
3E
2E
6E
B2u+ 4 %
u+Al
2u
PA2
Ap+
B2g+ B2U+ 3Eg+ 3EU

BZu+ 2 E
2B
A2
6E
B2"+
A1
Ag
Ax
3E
2E
3EU
5"

TABLES 208-278

2OB
24B
Djd
DF
continued
site
Representations
C1
3A
gl
ci
A
U
'l+
C2
A1$
Alu
2A
+ U+AI
2A + 2AZu+ 3E
2g
6'
+ U+AI
2E
AZu+
28
25B
A2+ B2+ E
+l
E2
Dj( 3C;)
A2+ B1+
E2
'6
A1
D6
A2 + El
EU
EU
AZu+
1g
EU
3A2+ 3B1+
++
(ad)
3B2+ 6E1+ 6E2
2B2+ 4E1+ 2E2
2B1+
2Al+
++
2Al+
A2+ B1+
2Bl+ B2+ 3El+ 3E2

2B2+ >El+ 3E2
C6
C2 v
Representations
A1+
c:(o,)
c:
21B
+ A2 + '2E1
3A1+
C2
%u+
E
+l
C6"
C1
B1+ B2+ 2E1+2E2
A2+
D3(3C2)
Site
AZu+ E
2EU
A2u+ 2EU
+
2g
D3d
1g
c3.
3E + 3Eu
2AZu+
2g
+ 3EU
Representations
A
c3
3EU
u
A
+l
D3
Ig
A
u+
l
c3
3AZu+ 6Eg + 6EU
i 3%g+
>Azu + 6EU
c5
'2
+ ?A
ul
Site
site
Representations
C1
3A
!:
+ 3B + 3E1 + 3E2
2B
2E1
c3
E2
A+B+E1+E2
A+E1
A1+
Bl+ B2+ 2%+
A1+
A2+ B1+
E2
B2+ 2E1+ 2E2
c;"(a")
A1+ B1+ El+ E2
Cdjv(ad)
A
+l
'6
A1
'6"
A1
B2+ El+ E2
A2
2E1
El
'3h
23B
3A*
3A"
2A'
A"
A'
A"
A"
E'
+
+
3Ev
E'
2E'
3E"
E"
E"
a6h
Site
C1
Ci
C2
CS
'Ph
c'
Representations
)A
TAU+ 3B
3Bu+ Xlu+ 3EZu
3Au+
A
2A
+ 3BU+ 3Elg+ 3Elu+ 3EZg+ 3E2u
Au+
2B
2BU+ 2E
2BU+ E
Au+
2Bu+ 2Elu+
Au+
1g
2Eul+
+ 2Elu+
1g
2g
E2,
2E
263+ EZu
EZu
c3
27B
AU + BU + ElU+ E 2 u
6'
'6
3h
Dsh
Site
A,
Elg + Elu
AU
Elu+
C1
E
2&
Representations
3A
+
'6h
4,
D6
Site
C1
C(;C);
Representations
3A1+
U
3
A
+
l
3$g+
3Blg+
3A2u+
3B2$
U
3
B
+
l
3BZu+ 6Elg
6~~~ + 6E2g + 6 4 u
ElU
ci
24B
18
3A2+ 3B1+
3B2
6E1
c:(c;)
A+l
A?+ 2B1+
2B2+ &El+ 2E2
C2(C2)
A1+
2A2+ B1+
?B2+ 3E1+
3E2
c;(c;)
A+l
2A2+ 2Bl+ B2+ 3E1+
3E2
D2
%+ B1+ % +
2El+
6E2
3A2,,+
3Aul+
3Blu+ 3B2"+ 6Elu+ 6EZu
1g+ A 1u+ A2g+ A2u+ 2B1g+ 2Blu+
2BBng+ 2BZU+ 4Elg+
4Elu+
2qg+ 2 q U
C2(C2)
1g
A
u+l
3%
C(;c);
2%
+ 2A2,,+ B
1g
Blu+
2B
2g
2BZu+ E'$l
3E2g+ 3%
163
Alu+ 2A
2g
2A2,,+
2B
1g
2Blu+
B + B2u+ 3E
1g
2g
)Elu+
3E2g+ 3E2u
C:(ah)
2A
1g
A
u+l
2%
AZu+ B
18
2Blu+ B
28
2BZu+ 'Elf

TABLES 276-318
D6h
278
29B
continued
Site
Representations
site
c;(u,)
&El,,+
4E + 2%,
2E
PA1$
lU
C1
B + 2BlU+ 7B2$
1g
2A7u+
2g
B2U+ 3E
Ci
Alu+
18
3ElU+ 3 4 $
c2
+ 2%U+ 2B + Blu+ B2g+ 2B2u+ >El$
AZg+
Cz
2 v (Cz+u
2 Y+ud )
c2v (c2 +ah+av )
c' (cy+o +a )
2v 2 h d
D2h
A2u+ Blu+
2BZU+ 4ElU+ 2EZu
BIU+'B;,u+
16
1g
+
2g
lU
+
lg
BZu+ 2EIu+
A
2g
A2u+
D2h
2E
2ElU+ E
(",
3C* )
A*,,+
lU
28
2u
2g
h'
FU
2ElU+ 2E7g+ Eau
2Elu+
It3
+
2g
TE
I&
BIU+ B-c g+ BZu+ 2E1$
c;"(""
+
1u
Aau+
BIU+ B + E + Elu+ E + E2,,

2g
I&
2g
I&+
AZu+
4 2u+ Blu+
6'
'3h
'6h
D6
'6"
+ Alu+
1u
+
26
+
1g
hlu+
E
+
1"
+
2g
Alg+ A
D3h(3c7+30,)
E + E I U + E +EZU
1g
2g
ElU+ EgU
A
A2,,+
3FU
Eu+ 3Fu
FU
Site
Representations
C1
3A1+
2E
5F1+ 5F2
A1+
A2+
C$(C*)
A1+
7A2+
D2( 3 4 )
3F1 + 3F2
D;(Cg+2c2)
A2+
3Fl+ 7F7
c4
A1+
3Fl
D4
2F1
F2
2 E + 2Elu
1g
262
3A2+ 6 3 + 9F1+ 9F2
C7@)
B + 2Elu+ 2E
2.s
)B 0
B2u+ E + Elu+ E + EpU

I&
2g
Djd(3C;+3a,)
EU+ 3F
2Elu+
EZg+ E2,
%u+
Azu+ B2u+ Elu+ EzU
Au+
EZU
2EZu
Dj( 3C; )
Dxd(3C2+303)
E2,
+ A + B + B +
2g
7u
1g
lU
+
164
Eu+ 4Fg+ 5Fu
2F + 3Fu
k!
BZu+ E
BIU+ B2u+
2E
5Fu
3FU
Au+
+ BZu+ Elg+
'6
2ElU+
Blu+
B78+ B2U+ 2 E1s+ 2ElU+ E2s+ EZU
2g
2E + 2E7U
7g
'6
Eu+ 5F$
Eu+ 5FU
c3
2g
+
2u
c2 Y
Ezu
BlU+ B
A7u+
A
3Ezu
BIU+ B + Izu+
2g
l g+ A2u+ B l g+ Blu+
2g
3Fu+ 3FU
AIU+ 2A2u+alU+
BZU+ >EIU+ 3EZu
D2
c;h(C$+uv)
PA
Au+ E
Au+
hiU+ 2AzU+
+
+
lg
'2h
C2h(Cz+ud)
lg
3AU+ 3EU+ 9Fu

A
3E2U
7Blu+
3Eg+ 3EU+ 9Fg+ 9Fu
>Au+
cs
AIU+
+u+
2-3
c&(c2ah)
A7u+
Representations
3A
16%
3ElU+ >EZg+ 3EZU

7A
T,
D3
A1
A2
A2
F2
2Elu
E1g+ El"
F1
3E
5F1+ 4F2
2F2
2E
3F1
7F1
F2
3F2
+ E + Elu
2"
1.3
BZg+ ElU+ Epg
Djh(3C$+3ud)
A2"+
B1g+ Elu+ E2g
D6 h
A2"+
E1u
318 Td
Site
c1
C2
Representations
3A2+ 6E
>A1+
A1+
2E
A2+
9F1+ YF2
5F1
5F2
Site
C1
Representations
3A
3E + 9F
cs
D7
s4
3F1
A2
)E
4F1
A + E + 3F
D7 d
A1
2F1
3F2
A2
2F1
3F2
iF2
3F1
3F2
3F~
A1
A2
5"
Al
F1
F2
Td
F2
3F2
I
C2"
c3
2A1+
2E
F1
2F2

TABLE 328
Oh
Representations
Site
3A1g+ 3Alu+ 3A28+ 3APu+ 6Eg+ 6Eu+ 9Flg+ 9FlU+ 9Fzg

gFzU
3Alu+
A
3APu+ 6EU+ 9FlU+ 9FZu
AIU+
16
1s+ Alu+
2A
2A
Alu+
PA
Alu+
1g
Al
2%
1g
Alu+
+
263
3E
2AZu+
2B
4FP,
5Flu+ 4F + 5F21
+
18
5Flu+ 5F2g+ 4F2,
3Eg+ 3Eu+ 4 F
2%u+
5F2u
5F2$
3Eu+ 5F18+ 5Flu+ 4F
A2u+ 4Eg+ 2EU+ 4 F
28
265
2EU+ 5Flu+ 5F2u
A2,,+
BEg+ 2EU+ 5F18+5Flu+
AZg+ %u+
3Eu+ 5Flu+ 4FZu
2%+,
3Flg+ 3FlU+ 3PZg+ 3FZu

A2$
%u+
Eg+ Eu+ 3F
A1$
kzg+
23
A2,,+
1g
1B
c4
,4'
1g
+ EU+
2E
AZu+
2F
2F
2F
26
3FlU+ 2F
>FpU
2g
>Flu+ 3F
18
28
+ Eu+
2F1$
2FZu
2F2U
3FlU+ 2F
267
2F2u
Eu+ 3FlU+ 2FZu
+
1g
Alu+
s4
)Flu+
3F~u
AZU+
A
2B
"lU+
D;,($+Z$u$2~&
16
E + Eu+ 3F + 3Flu+ 2F + 2F2u

g
1B
2s
1u
+ Eu+
2g
3FlU+ 3F
2F
16
28
2FZu
Eu+ 3Flu+ 2FZu
lU
2F + 2Flu+ F + F2,,
h3
26
c4 Y
1g
F + 2Flu+ F + F2u
1.s
2g
DZd(X:+od)
F1g+ 2Flu+ 2F28+ F2u
bd
(C2+2C2+0,,)
4
4' h
D3
C3V
E + F + 2Flu+ F + F2u
8
1g
2g
2FlU + F2u
A
'6
2.3
1g
lU
2g
A2u+ 2E
Alu+ AZu+ 2Eu+ ?Flu+

A
+ Eu+
A2u+
A2u+
E + Eu+ F
Flu+ F
1.3
'3d
Th
Flu
F1g+ Flu
Td
Flu
Oh
Flu
2u
1g
2EU+ 3F
1g
3Flu+ 3F2$
3F2,,
3FZu
2g
2F
1g
1g
2Flu+ F
F2,,
2Flu+ 2F
F2u
2g
2B
2F + F2,
1u
+ FZu
2g
F2u
Fa3
D. L.. ROUSSEAU, R. P. BAUMAN AND S . P. S. PORT0
Tables C. Librational lattice modes of polyatomic units when placed on each of the possible sites in the unit cell
Site
C1
Re resentations
3c
1g+ Blu+ 2B2.3+ 2B2"+ 2B2t 2BJu
Au+
2B
C,X(C,x)
Au+
2Blf
C:Y(qXY)
2Au+
B16+ 2Blu+ 2B2b3+ BZu+ 2B33+ B3u
C;"(OXz)
2Au+
2 81g+ Blu+
CY(0YZ)
2Au+
2B + Blu+ 2B + Bzu+ B + 2BjU

18
2R
36
ci
)Ag+
C~v(C~+oxz+oyz)
Au+
B + B + B2u+ B3g+
16
26
3B
C:b(C:+~xy+~z)
+,A,
B
16
C~r(C~:t,v+oxz)
A"+
B
16
D2
B1gf B l U
4c
cs
Site
Hepresentations
c;h(C~+nw)
I
_
C?&(C;+O~')
C2xh(C3d")
As+
D2h
B16+ B2 g+ B 36
16
2Blu+
2B + 2B2u+ B + B
2g
3e
3u
BTu
B3g+ BJu
B2u
2B + B + 2B
16
26
2BgU
BJu
Blu+ Bzg+ BzU+ BJg
B2g
36
B2g C 2B2,i+ 2B3$
2g
2B
BzU+ 2B
BlU+ B
B + 2 8 + 2Bx
16
26
3BBjg
2g
2Blu+
7B2f
3B1$
mepresentntions
3B2u+ 3BJg+ 3B3u
3BlU+ 3B2$
Au+ B
c2
A:
3Au+ 3B1$
$(C:)
c:
3A
A
c;(c:)
zc
Representations
379
B3u
2Bpg+ B
16
Representations
?AAu+ 3Bg+ ?Bu
!A$
i~
I
!Ag
"2
Au+
2%+
2B
2B
2BU
Bu
3B
3E
+ B+2E
A + E
cs
ZB
1oc
I
11c
Sh
site
Representations
c1
3A
c2
A + B + P E
c2
cs
1981
3E
Cirh
i'
OF RAMAN SPECTROSCOPY, VOL. 10,
3B
A +
C1
JOURNAL
s4
site
274
3A
3Bg
Representations
)A
3Au+ 3Bg+ 3Bu+ 3Egt 3Eu
Xg+ ?Bg+ 3Ep

A
Au+ B
?Au+
BU+ 2E + 2 E U
2Bu+ 2 E
c2 ti
A g+ Bg+ 2ER
c4
Au+
s4
Bu+
+ EU
'4h
A + E
6
6
E
,,
Eu
TABLES 12C-19C
LIBRATIONAL LATTICE MODES

rC
Site
Representations
C1
3Al+ 3A2+ 3El+
CX(C:)
A1+
A2+ B1+ B2+ 4 E
C2(C2)
A1+
2A2+
Cgci)
A1+
2A2+ 2B1+
D2(C22C2)
%+ B2+
2E
D$(C$+PCb)
%+ B1+
2E
2E
A:,
D4
13c
A1+
c4
3B2+ 6 E
B1+ 2B2+ 3E
B2+ 3E
Representations
C1
3Al+ 3%+ 3B1+ 3B2+ 6 E
%+ B1+
Al+
++
B1+ 2B2+ 3 E
c:('Td)
A1+
2%+
2Bl+ B2+ 3E
C2yJ'T")
A2+
B2+ 2E
Qa)
A1+
c4
c4
++B1+
"
A2g+
D;(C:+2C;)
C~y(C~+2ay)
Alu+ A2$
C&(Cz+20d)
Alu+
CZv(C2%fud)
Alu+ A
C~y(C;+oh+od)
Alu+
2E
Bag+ B2u+ 2E6-
ASu+
2U
Blu+ B2g+ 2 Eg+ 2Eu
B + B2u+ 2Eg+ 2Eu

1g
AZu+
2g
2g
%+ 2E
+ B
+ 2 E
26
g
+ B
+ZE
1E
8
2.3
c4
A 1g
213
A 1u+ A2 g+ A2u+
A +
2g
1g
+ A
lg
+ A
+ 2 E
2E
AlU+ %g+ Eg+ EU
Did( Cg+2Ci+oy)
D2d(C~2C2+~d)
A
2g
D4h
A2g
Site
Representations
+ Eu
2E
2Eu
C4"
28+
Eu
+E+EU
2u g
D4
2g
Blu+ BZu+ 2E + 2EU
3A
Representations
3B1+ 3B2+ 6 E
3A2+
A2+ B1+ B2+ 4 E
CZ(C2)
A1+
2A2+
cs
A1+
2A2+ 2B1+
D2
A2+ Be+
D2d
B 1g+ Blu+ B2U+ 2 E
Dih( c;+zc; )
C1
A+
l
s4
BZu+ 2 E
EU
Blu+ E
Eu
B2,+
Eg
% + E
>Al+
"
2g
2E
C;(C;)
c2
Blu+ B
qZE+ ASu+
A2+
A1+
A:,
A2+
3E
c
17C
B1+ 2B2+ 3 E
B2+ 3 E
2E
B1+ 2E
A + E
c3
C1
isu
Blu+ ZEg+ 2Eu
1g
'4h
D2d
Site
D:,(C22C2)
s4
B2+ 4 E
C:(O,)
C:"(
Representations
D2 h( C 2 2 C:, )
Site
A1+
continued
Site
cqy
C2
Dllh
Sg
Site
Representations
Cl
3A + 3Au+
C.
3Ag+ 3Eg
C3
2E
'6
Au+
3Eg+ 3Eu
Eu
a + E
g
Site
3A2+ 6 E
>A1+
A1+
19c
A2+
2E
cJv
Site
Representations
Cl
>Al+ >AAp+ 6 3
A1+ 2A2+ 3E
A ~ +a*+ ZE
5"
0Heyden & Son Lttf,
1981
a2 +
D. I-. ROIJSSEAU, R. P. BAUMAN AND S. P. S. PORT0

LIBRATIONAL LAlTlCE MODES
TABLES 20C-27C
2oc
24c
Dx
Site
3AlU+
1g
2g
'2h
+
1g
2A
2%
+
?g
3Eg
+
2g
'3
A
A
1g
lU
'6
Ale;+ %g+ 2 E g
D y 3c;
A2u+ 2Eg+ 2 E U
A1+
'6
A2
El
Al+
%+ 2B1+
2B2+
A1+
2A2+ B1+
2B2+ >El+
Al+
2A2+ 2B1+
2B
%+ B1+
E2
2%+
2%
3%
3q+ 3%
B2+
B2+ 2 5 + E,,
%+ B1+
A1+
A + B + El+
B2+ 2E1+ 2E2
% + B 2 + 5 + 4
A1
B1+ El+
A2+
+%+
2E1
.c,
Site
A2
Representations
3A1+ 3A"
3E'
A'
2A"
E'
A'
A"
A'
E"
+
+
E'
C1
Ci
26C
2E"
C2
CS
'2h
c3
'6
AU+ 2B
2Au+ 2 B
+
g
c:(uh)
Ai
2A;
A;
cI(a,)
Ai
2A:
2AS
C2"
A;
A;
A;
El
2E"
c3
Ai
A;
A;
A;
PE'
D3
A;
A;
E'
E"
c3"
A;
A;
E'
E"
cm
A;
A$
2E"
A;
E"
3EpU
+
1g
2Bu+ 2 E
Bu+ 2 E
2ElU+ Em + Epu
d.3
+ Elu+
+ 2EZu
28
18
2B + 2 E + EZg
g
1g
Au+ B
+ BU+
+
1g
E+,l
2g+ E2,
'3h
2A;
A;
2E'
4E"
3E'
3E"
2E"
&
A + B + E + E
g
g
1g
28
u+ E14+ Elu
t A
27C
'3h
,D
3Bg+ 3Elg+ 3EZg
'6
3ElU+ 3E2$
3Ag+ 3Au+ 3Bg+ 3BU+ 3E1$
El
E"
Representations
?Ag+
3E"
C6h
Site
45+
+ 3 B + 3%+ 3%
3A
23C
3B2+ 6E1+ 6E2
3A2+ 3B1+
Eg
Representations
22c
E2
A2+ 2E1
3A1+
54
Eg+ Eu
A2g+ %u+
%g
E2
B2+ El+
A2+ B1+
'6
E2
A2+ El$ B2+ 2E1+ 2%
A1+
D~(3c2)
AzU+ >Eg+ 3Eu
B2+ 2E1+
A2+ B1+
c3
3Eg+ 3Eu
2AZg+ 2A2u+
A + 2Alu+
1g
CS
3 A 2 b 6Eg+ 6Eu
>A2$
D2
"\lu+
Alg+
C2
Representations
3A + 6Eg
3Alg+
C l
continued
Slte
Representations
3A
C1
D6
A +
D6h
B + E + Epu
u
1g
Representations
iAg+
24C
D6
Site
Cl
C:(C;)
C i
A2+ 2Bl+ 2B2+
3A1$
kEl+ 2 E 2
C2(C2)
A
+
C2(C2)
Al+ 2A2+ B1+ 2B2+ 3EL+ 3E2
CgC;)
Al+.:2A2+
Cp;)
276
2B1+
B2+ 3El+ 3E2
JOURNAL OF RAMAN SPECTROSCOPY, VOL. 10, 1981
1g
163
3B
%g+
lU
+ 3B + 6E
1g
+u+
AIU+ A2$
TBzU
6Elu+ 6 E + 6%u
26
1g
2g
6E2g
2 B + 2Blu+
1g
'sg+2%u
45g+
"lU+
?A1+ PA,+
3B1+ 3B2+ 6E1 + 6E2
A,+
6Elg+
Hepresentations
3Blg+ "Iu+ 3B2$
3Alu+ 3 5 g +
3Alg+
2%
1g
Blu+
2 B + 2B2,
2%
2B2g+
2B2u+
3Elg
3E1u+ 3%g+ 3%
1g
Alu+ 2 A
3Elu+ 3%'
2g
2%,+
2B
1g
2Blu+
+ B2,+
25
3E
15
3E2u

TABLES 27C31C

continued
Dr.
Th
~~
Site
Site
Representations
A
2B18+ Blu+ 2 B2g+ Bau+ 4Elg
A 2B+ 2$u+
2Alut
1g
'9u+
2%'
"u
2Alu+
2$g+
C1
Ci
1g
A 1g+
'Alu+
%&+
Alg+
Blg+2BZg+
+
lU
Big+
B2B+ BZu+ 2 818+ 2ElU+ E2$
%u+
B + B
1g
2g
Alu+
%E+
APu+
B + Blu+ B
1E
2g
Alu+
2g
1g
+
2g
+ %
AZg+ %u+
Blg+
+
2u
AIU+
Alu+
28
+ B
IE
+
18
Alu+
AZg+
+
2g
c3
Eg+ 5Fg
D2
3Fg + 3Fu
EU+ 5F + 5FU
2Eu+ 5F
Eu+ 3F
Au+
4Fu
2Fu
3Fg
'6
Ag+
Th
Pg
Au+ E
Eu+ >Fg+ 3Fu
Eg+ P g
FU
C1
Elu+
E2u
E2g+ E2u
2EZu
BlU+ El$
9F
A + E + 5F
3P
%+
6E
PE
9F1+ 9F2
+ 5P1+
C& (C2)
A1
D2(X$
3Fl + 3F2
D&(Cg+2C2)
%+ E +
3F1+ 2F2
3F1+ 2F2
D4
'PI
F2
c3
A1+
++PE +
3E
2%+
A1+
5F1+ 4F2
3Fl+ 3F2
%+ E + 2P1 +
F1
5F2
P2
FP
F1
El,,
31c
Ta
Site
Representations
C1
3Al+ yL2+ 6E + 9F1+ 9 4
E2u
1g
"2'
3Al+
A1+
D3
El&+ E l u
Representations
C2($
c4
+2E
1.8
3E
4$ EZu
AZU+ 2Elg+ 2Elu
Representations
28
2g
+ E
'2h
2E
pg+p u + %g+
BZu+ E1g+
A2 g+ BZu+ E1g+ E2U

A2g
+
1E
Blu+ BZu+ 2%
A2g+ E18+
Alu+
D2
)C
1g
1g
%g+ %u+
3A
2Elu
+ E +E2g
2%u
+EZg
Ig
+ A
1g
BZg+ 2E
BlU+
1g
+ E
2g
2g
%g+
2g+ Bl U+ B2g+ E1 g+ EIU+ E2g+ EaU
+ B
El,,+
Blu+ B28+ BZu+ 2E1$
B2g+ BZu+ Elgt Elu+

Blf
+
g
9F
PAU+ E
Site
+ B I E+
2g
A2g+
2%
1g
Azu'
BZg+ 2E
A 2g
BZu+ 2Elg+ Elu+ E2g+ 2EZu
3E
c3
EZu
2%
+
18
1g
%
I
2' h
2 E l b %g+
?Au+ 3Eg+ 3Eu+ 9Fg+ 9FU
Au+ E
c2v
BlU+ Bzg+ B2u+ 2Elf
+B + Blu+
2g 1g
2%g+
c2
3%g
%&+
C1
3Elg+
3A
ca
4E1g+ 2%g
Alu+
Site
B1g+ 2Blu+ 2B2s+ BZu+ 3E18
3A
C2
B2&+3E1g+ 3 E ~ g
2%g+%g+
%g+ %u+
Blu+ BZ8+ 2BZu+ 3E16
3%
2Blg+ 2B2$
A163+ 2+$
"I&+
%u+
2Aag+
3Elu+ 3%g
2Blg+
YU
TElU+ 3%g+
%u+
Representations
C2
A1+
%+ 2E +
cs
A1+
2%+
3E
5F1+ 5 4
5F1+ 4F2
D2
3Fl+ 3F2
c2v
%+ E +
3F1+ 2F2
3F1+ 2F2
s4
A1+
2' d
2Fl
F2
A + E + 3 F
c3
C3V
A1+ A2+ 2E
%+ E +
3P1+ 3F2
2F1+ F2
p1
Td
p1
PP
TABLE 32C
32c
Oh
Site
Representations
3~ + 3
C1
~ 3 ~ ~ ~3%,,+
~ + ~6Eg++ 6Eu
1g
9Flg+ 9Fl,,+ 9F2g
9F2u
3A 1g+ ,A2$
ci
C2($
Ci(C2)
c:(uh)
C:(Ud)
A
A
A
CEg+ 9F1$
A~"+ A
Alu+
2A
'+
2Alu+
1g
16
1g
2A
1g
33 + 3Eu+ 5P + 5Flu+ 4F;g+4F2u

1.3
2AZu+
2E
AZu+
3E
+ 3Eu+
2%
2g
2E
Cib(C2+od)
A 1g+ 2+g+
D2 ( 3Cf )
3F1$
D;(C:+2C2)
$&+
A2u+
Eg+ Eu+ 3F1$
C&(C2+20,)
Alu+
AZu+
2Eu+ 3F
C:y(C:+2~d)
Alu+
C' ( C +a +o )
2 v 2 h d
Alu+
Aag+
D2h(XE+%h)
Ylg+ 3F2g
D;h(C~+2C;pn2u,,)
c4
$4
4' h
c4
"
A2u+
C3"
Djd
2Eu+ 3F
1g
3F2u
2Flu+ 2F
2g
2F2u
2F2u
+2F
26
F2g+ FzU
2g
2Fp~
Eu+ 2F18+ Flu+2g+ F2u
1g
Fag
%&+
1g
1g
%u+
Alu+
2g
2E
28
A,, g+
23
Eu+ 2F1.3+ Flu+ Fa3+ F2u
AIU+
A2u+
D3
2Flu+ 2F
263
1g
E + Eu+ 3P + 2Flu+ 2 F + 3F2u

193
28
D ' (C2+2C2+sh)
2d 4
'6
2Flu+ 3F + 2P2u
2g
+E + 3 F
3FlU+ 2F28+ 2F2u
+ E + Eu+ 3Flg+ 3Flu+ 2F'
lU
ZF1.3+ Flu+
c3
5F2"
Eg+ 3Flg+ 2F26

A
1g
2F
Eu+ 3F
A2u+
D2d(3C:+od)
D4h
4Flu+4F2$
3FZu
h3
2 F1s+ 'Flu+
D4
1g
3Eg+ 5E18+ &Fag
2g
1-6
5F
I&
3Flu+ 3F2$
+&+
A
4EU+ 5F + 4Flu+ 5F + 4%
I&
2g
5F + 5FZg
26
2EU+ 5Flg+ 5Flu+ 5F28+ 5F2u
2AZu+
Cnh(C:+uh)
1.3
2g
2A
lU
2E
AZu+
2g
9FZg
3F
2Eg+ 2Eu+ 3F1$
3FlU+ 3F26+ 3 F a
3Fpg
Eu+ PF 1g+ 2Flu+ FPg+ F2"
Eg+ Q+ 2F + Flu+ F2g+ 2F2,,

I&
2g
A2u+
2F
1g
FPg
F1g+ Flu+ F2 R+ F2=
Th
F + F
1g
2g
Flg + F l u
Td
F1g + Fzu
Oh
Tables D. Correlation tables relating the irreducible representations of each point group to the irreducible representations of each
of its subgroups
C.
1D
C.
20
6D
~~
A,
AU
AU
A"
A'
D~~
c1
A
A
,
B1g
B2g
B2U
B3g
ciY(exY)
c:'(ox2)
c~~(&'~)
ci
A'
A'
A'
A"
A"
A"
AU
A'
A"
A"
A"
A'
A'
A"
A'
A"
A'
A"
A'
AU
A"
A"
A'
Ag
A'
A'
A"
A"
c:(cg)
B3u
c1
c2
c,xz(a;~) C F ( U 7 )
A'
A,:
A"
A"
B1
A'
A"
B2
A"
A'
A'
c:(cz)
c;(cX)
BlU
C2"
A1
Ag
4,
Ag
D . L. ROUSSEAU. R. P. BAUMAN AND S. P. S. PORT0

CORRELATION OF EACH POINT GROUP TO ITS SUBGROUPS
17D
'4h
Ag
1'
1'
'2
5'
'2h
AK
A'
AU
A"
A,
Ag
A'
Ag
A,
A"
A,
2A
2Au
28
2A"
2Bg
2A
2Au
2B
2A'
2Bu
4'
'4
SL
AU
?A
7Ag
E"
?A
PAU
Ag
A"
AU
El3
EK
BU
Eg
Ell
18D
D4
c;(c;)
-lc
A1
14.
B1
B2
C2(C2) C$(C&)
(CE+2C2)
81
B1
B1
81
2).
2~
A+B
A+B
BZ+B3
B2++B,
D,
c4
(C;+2C$)
8-
2A
A+B
1
D3d
Alg
ZA
?B
A'+A"
A'+A"
B1+B2
B1+B2
Alu
Eg
C?"
A
A'
A"
B1
A"
A'
ZA
2B
A+B
A'+A"
A1
A2
A2
B1
A1
B2+B,
B1+B2
Eu
1
s4
1'
1'
'7
's
'2h
Ag
A'
kg
A"
, ,A
'
j
CJ"
*l
A1
A1
A2
AU
AU
Ag
A"
Bg
A2
A2
AU
A'
BU
AU
A2
A1
?A
2Ag
A+B
A'+A'
A +B
?A
?AU
A+B
A'+"'
A$Bu
EU
1 2 6
EK
21D
C,
?A
2B
15D-see opposite
16D
C,
A"
A"
2A
280 JOURNAL
2A'

TABLES 15D
15D
D&h
Alg
Al"
A2g
A2u
B1 g
BlU
B2g
Bzu
Eg
'2h
(c2+av)
'$h
(';+Od)
A'
A
g
Ag
Ag
A"
A"
A
,
AU
ci
cg(cf)
cz(c2)
Cb(ci)
c:("h)
c:(av)
c:(ud)
Ag
A'
A'
AU
A"
Ag
A'
A"
A"
Ag
Bg
Au
A'
A'
A'
A
,
Bu
Ag
A'
A'
A"
Ag
A"
A'
AU
Ag
All
Bg
BU
Ag
Bg
4,
BU
BS
A8
A"
A"
Ag
A'
A"
A'
A"
A"
A'
A"
A,
B"
AU
2A
PAg
2B
A+B
A+B
2A"
A'+A"
A'+A"
2Bg
Ag+Bg
A +B
g g
2Au
2B
A+B
A+B
2A'
A'+A"
A'+A"
2Bu
A"+
Au+Bu
2A
Eu
'fh
(c2uh)
c1
D,,,
l5D
Eu
B,
cmtinued
Eu
D. I>. ROUSSEAU, R. P. BAUMAN AND S. P. S. PORT0

TABLES 23D-260
2 3D
'6h
EZg
EZu
'6h
'2
's
Ag
A'
AU
A"
1'
i'
'3
'6
6'
'3h
Ag
A'
Au
AU
A"
'Ph
Ag
Ag
A"
Bg
Ag
A"
AU
A'
Bu
AU
A'
2A
2Ag
2B
Eg
El
E"
2A
2AU
2B
2A'
2Bu
Eu
E'
2A
2Ag
2A
2A'
2Ag
Eg
E'
2A
2Au
ZA
2A"
2Au
EU
E:,
E"
2Bg
A2
B1
A2
A2
B1
B2
A1
A2
B2
Bj
A2
A1
2A
2B
A+B
A+B
B2+Bj E
El
2A
2A
A+B
A+B
A+B1
E2
12
El
E2
1
c6v
A1
+
B1
B2
El
Eg
2A"
'1
cp
cI(Ov)
A'
'6
'2"
c3
A'
A1
A1
A1
A"
A"
A2
A2
A2
A'
A"
B1
A1
A2
A"
A'
B2
A2
A1
2A
2B
A'+A"
A'+A"
B1+B2
El
2A
2A
A'+A"
A'+A"
A1+%
';v(OV)
c1
'2
c:(oh)
c:("v)
C ~ V
3'
Dj
'3"
'3h
A'
A'
A1
A1
A1
A'
A"
A"
A2
A2
A"
A'
A"
A'
";
A"
A'
B1
Az
A1
A"
E'
2A
A+B
2A'
A'+A"
A1+B2
E'
E'
2A
A+B
2A"
A'+A"
%+El
E"
12
D-y,
A i
A;
282 JOURNAL. OF RAMAN SPECTROSCOPY,VOL. 10, 1981
A
A
@ Heyden & Son Ltd, 198 1

TABLES 27D
A
A
A
A
A
A
A
Elg
ElU
E2g
27D
A'
A'
A'
A"
A"
A"
A'
A"
A"
A"
A'
A'
A"
A"
A'
A'
A'
A"
A"
A'
A"
A'
A"
A'
BU
BU
AU
A%
AU
Ag
Ag
AU
Ag
Ag
AU
AU
Ag
Bg
AU
BU
Bg
Ag
BU
AU
Bg
AU
2A
2Ag
28
A+B
A+B
2A"
A'+"'
Ar+A"
2Bg
A +B
2A
2Au
2B
A+B
A+B
2A '
A'+"'
A'+"'
2BU
AU+Bu
2A
2Ag
2A
A+B
A+B
2A I
A'+"'
A1+A"
2Ag
Ag+Bg
Dc.
cantinved
/I
1%
A1
A1
Alg
A 1g
A'
Ag
Ai Ai
Ai
Ai
A2
A2
Aul
Alu
A"
Au
A1
A;
A;
A2
A2
AZg
Apg
A'
Ag
A2
A2
A$
A6
A1
%u
A2u
A"
AU
A2
A1
A;
A;
A2
A,,
Agl
Azg
A"
Bg
B1
B2
A!
A;
A1
A:,
Aul
Agu
As
8,
Bl
B1
Ai
Ad
A1
A2
A 2g
A
gl
A"
Bg
B2
B1
A:
A;
A2
A1
AZu
Aul
A'
B,
B2
B2
A$
Ai
Eg
El
E"
Elg
El
El
E"
E'
EU
El
E'
Elu
El
El
E'
E'
E6
E2
E'
E2g
E2
E*
4u
E2
E2
E"
E"
14
A2
A1
E2u
1
53
EU
Eg
Eu
EU
E'
D. L. ROIJSSEAU, R. P. BAUMAN AND S. P. S. PORT0

TABLES 280-32D
28D
29D
T,
Ag
A'
A
,
A"
2A
2Ag
2A
2A'
2A
2AU
2A
3A
3Ag
F,
3A
24
As
A
,
?A
A+2B
B1+B2+B3
A+E
Eg
E,
Fg
A1
A6
A2
A"
Au
2Ag
2A
2A1
2A
E8
2A"
2%
2A
2%
2A
E"
A+2B
A'+2A"
Ag+2Bg
B1+B2+B3
"2cB1+B2
Blg+B2g+Bjg
A+E
A K+E g
3A,
A+2B
2A'+A"
AU+2Bu
B1+B2+B5
A1+Bl+B2
Biu+B2u+B3u
A+E
Au+E~
12
12
12
Ag
All
Ll
Di
0
A1
%
Ch
D4
C?
D3
A1
A1
81
Bl
A2
C1
C2(C:)
CQ(C2)
D2(3Cf)
(Cg+2C2)
2A
2A
A+B
2A
A+B1
A+B
A1+B1
F1
3A
A+PB
A+2B
B1+B2+B,
B+
l B2+B,
A+E
++E
A+E
A2+E
F2
1
3A
A+2B
2A+B
B+
l B2+B3
A+B2+B,
WE
B2+E
A+E
A1+E
24
12
12
%d
'3
A1
A2
B1
ZA
A1+A2
A+B
A1+B1
A'+2A"
Bl+B2+5.,
A2+B1+B2
A+E
A2+E
A+2B
2A'tA"
B1+B2+B3
A1+BL+B2
IKE
B2+E
12
12
'2h
'2h
c1
c2
CS
D2
A1
A'
A2
A"
2A
2A
A'+"'
F1
jA
A+2B
Fp
3A
24
"
'4
*d
c2
A1
c1
c1
c2(c$)
c;(C2)
C:(oh)
ci(qd)
A'
A'
A"
A"
A'
A"
(Cf+ah)
Ag
AU
A2g
Ag
A2u
A"
A'
A'
Eg
2A
2Ag
?A
A+%
PA'
A'+A'
Eu
PA
PAU
2A
A+!3
PA"
A'+A"
2AU
>A
>AK
A+2B
A+.?B
A'+EA"
A'+2A
A +PB
3A
>Au
A+PB
A+.'B
2A'+A"
?A'"''
3A
>Ag
A+%
2A-B
A'+2A"
A1U
FIK
Flu
FTg
'3"
A2
oh
A15
F
2
Ag
AU
AU
Ag
Bg
A"
BU
A +B
K
D2(3Cz)
(Cc+7C2)
B1
BI
"
2A
A+B1
Ag+2Bg
Bl+B2+Bj
B1+B2+B3
Au+2Bu
Au+2Bu
B1+B2+BJ
B1+B2+B
PA'+A'
A +PB
2Ag+Bg
B1+B2+BJ
A+B2+B3
2AU+BU
B1+B2+B3
A+B2+B3
12
12
12
3A
3AU
A+PB
7A-B
2A'+A'
A'+2A
Au+2BU
i
!
2,I
211
2L
24
24
i2
A+B1
AU+B"
FEU
(C2+od)
Ag
2%
D'

continued
Oh
F2u
TABLES 32D
c;
"
c;"
CZ"
(c2+20h)
(c$+2od)
(c2+ah+od)
(34+3'h)
(c:++2c2+oh+ad)
A1
A1
A1
Ag
Ag
A2
A2
A2
AU
A1
A2
B1
Ag
A2
A1
B2
2%
%+A2
2%
A1+%
D2h
%+B2
%h
c4
s4
AU
B1g
AL
B1u
2Ag
A +B
A+B
AiB
2%
%+A"
A+B
A+B
1g
1g+B 2g+B3g
A2+B1+B2
A2+B1+B2
A2+B1+B2
B 1g+B 2g+B
A1+B1+B2
A1+B1+B2
A1+B1+B2
Blu+B2u+B3u
Blu+B2u+B3u
A2+B1+B2
Al+Bl+B2
Al+%+B2
Blg+B2g+B3g
Ag+B 2g+B 3g
A1+B1+B2
A2+B1+B2
Al+%+Bl
BlU+%U+B3U
12
12
12
A+E
A+E
A+E
BtE
AU+%+B3U
W E
A+E
12
12
Bg
B1
B1
B1
B2
B1g
BU
B1
B2
A1
A2
BlU
Ag+Bg
A1+B1
A1+B1
A1+B1
A1+B2
%+A2
AlU+BlU
A2+E
A2+E
AZg+Eg
A+E
A +E
g g
+B
18
Ag
AU
E
1g
Au+Bu
A1+B1
A2+B2
Ag+Eg
A2+E
A2+E
A +EU
A2+E
A1+E
B2+E
B2+E
AZu+Eu
A+E
Au+Eu
Bg+Eg
B2+E
B2+E
B2+E
B1+E
B2$Eg
A+E
A +E
Bu+Eu
B2+E
B1+E
A2+E
A1+E
BZu+Eu
A+E
Au+Eu
EU
16
Oh
D3
'3"
D3d
Th
Alg
A1
A1
Alg
Ag
A1
A1
A2
AlU
AU
A1
A2
A2
A2
A2g
A2
A2
A2
A1
A2u
AU
A2
A1
Eg
EU
EU
F1.a
A2+E
A2+E
A2$Eg
Fg
F1
F1
Flu
A2+E
A1+E
AZu+Eu
FU
F1
F2
F2g
A1+E
A1+E
Alg+Eg
Fg
F2
F2
F2U
Al+E
8
A2+E
8
AlU+Eu
4
F
4
FU
F2
F1
A1u
A2U
Eg
EU
A1
Eg
A
A
E
Ag
Td
JOURNAL
OF RAMAN SPECTROSCOPY, VOL. 10, 1981 285
Tables E. Character tables.
7E
1E
YT
-1
RE
3E
Blu
c2
axY ax oYc
-1
-1 -1 -1
-1
-1
-1
-1 1 1
-1
-1 1 -1
-1
-1
1 -1 1
Selection
RZ
Selection R u l e s
X T i 3
-1
-1
RU~S
axy
TZ
Ry
axz
TY
10E
6E
*I1
R
286 JOURNAL

TABLES 11E-17E
CHARACTER TABLES
12E
11E
c2'
ZC,'
zc21i
2c2
S e l e c t i o n Rules
axx- ayy'axy
-1
-1
D4
I
3
XT
-1
-1
-1
14E
13E
C4"/
2C4'
C2'
20"
A1
A2
-1
-1
B1
-1
-1
B2
-1
-1
YT
-2
2od
l
a:,+
RZ
axx
axY
(T~.T~);(R~,R~)
(a;,,
a;,)
YT
2C4
Cgz
2C2
2CZ1
254
oh
20"
2od
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
0 - 2
2
0
-1
-1
-1
-1
-1.
-1
-1
-1
Selection
-1
Rules
1
1
1
-1
17E
'
S6
Ag
E
1
C3
Cj2
S6
S65
RZ

TABLES 18E-23E
CHARACTER TABLES
;%
19E
20E
21E
2%
*1g
*1u
2S6
-1
-1
-1
:Jj
1
1
*2
X:,
-1
-1
Od
-1
-1
-1
Eu
22E
Selection Rules
I
e = e?Ti/>
Selection R u l e s
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
-e*
-C
E*
-1
-1
-P
-c*
E*
-1
-1
-r.*
-E
c*
-1
-E
-C*
c*
-1
1
1
c*
e*
C*
E*
EX
C*
-1
E*
E*
-1
-1
-1
-1
-1 -1
1
E* -E*
-E
-E*
-E
-c
-Ex
.*
E
C*
e*
-E
-c*
-1
1
-1
:* I:
C
-C
-E
e*
:i
1
-1
-E
-C
-1

CHARACTER TABLES
TABLES 24E-27E
24E
3C2'
2C3
C2'
3C2
1 - 1 - 1
-1
-1
2Cg
-1
-1
-1
1 - 1
-2
-1
-1
2 - 1 - 1
-1
Selection Rules
"xx
"yy="zz
-1
25E
2C6
2 5
C2
>av
>ad
-1
-1
-1
-1
-1
1 - 1 - 2
0 - 1
2 - 1 - 1
1-
-1
26E
2C3
3C2
ah
2Sj
>av
-1
-1
-1
-1
-1
2 - 1
2 - 1
-1
2 - 1
0 - 1
Selection Rules
1 - 2
27E
E
2Cg'
2C3
C2'
3C2 3C2'
2Sj
2S6
Alg
Alu
-1
-1
-1
-1
-1
-1
-1
-1
-1
-1
ApU
-1
-1
-1
-1
-1
-1
Blg
-1
-1
-1
-1
-1
-1
El"
-1
-I
-1
-1
-1
-1
B2g
-1
-1
-1
-1
-1
-1
Bpu
-1
-1
-1
-1
-1
-1
Aeg
Elg
1 - 1 - 2
Elu
-1
-7
-2
-1
EZg
-1
-1
-1
-1
-1
-1
-2
-2
EZu
ah 3ad j a v
Dsh
Selection Rules
JOURNAL
OF
RAMAN SPECTROSCOPY, VO1. 10, 1981 289
D . L. ROUSSEAU, R. P. BAUMAN AND S. P. S. PORT0

TABLES 28E-32E
CHARACTER TABLES
2 RE
UC,,
45'
3C2
US6
4S6'
>oh
-1
-1
-1
-1
-1
30E
A1
--1
-1
A2
6s4 j c p
-1
-1
-1
8C3 6ad
1
axx+
YY
zz
I
I
290
JOURNAL. OF RAMAN SPECTROSCOPY, VOL. 10, 1981
+ a
xx
yy+ azz

Artigo Porto Normal Mode Determination in Crystals

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Artigo Porto Normal Mode Determination in Crystals

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SERGIO P O R T 0 COMMEMORATIVE ISSUE

Normal Mode Determination in Crystals

The current interest in phonon spectroscopy, which has

There are several methods by which the unit cell may

JOURNAL OF RAMAN SPECTROSCOPY, VOL. 10, 1981 253

D. L. ROUSSEAU, R. P. BAUMAN AND S. P. S. PORT0

correlation diagram." Such a set of tables (Tables B) are

Space groups, point groups and factor groups

OF RAMAN SPECTROSCOPY, VOL. 10, 1981

more than one center of symmetry, or where one C2

NORMAL MODE DETERMINATION IN CRYSTALS

SYMMETRIES AND SELECTION RULES OF

Factor group analysis

XT(R)= *1+2 cos &

or since within each class k, the x j ( R )are the same, Eqn

In Eqns (3a) and (3b), nj is the number of times the

within the Born-von Karman approximation, and

D. L. ROUSSEAU, R. P. BAUMAN AND S. P. S. PORT0

Here we adopt the usual convention in which the upper

Nuclear site group analysis

to the behavior of the three components of a vector.

Molecular site group analysis

NORMAL MODE DETERMINATION IN CRYSTALS

considerations of the groups giand G as for the nuclear

Selection rule breakdown in Raman scattering

0Heyden & Son Ltd, 1981

asymmetry, the selection rules will be modified, by

for a crystal in which there exists only one optical polar

I). L. ROUSSEAU, R. P. RAUMAN AND S. P. S. PORT0

may be made between the tensor component and the

TABULAR PRESENTATION OF SYMMETRY

F ) have four times as many points as the primitive lattice

NORMAL MODE DETERMINATION IN CRYSTALS

at about 120 "C. These two structures, each containing

Figure 2. Symmetry operations of the cubic phase, 0:'of barium

It is also illustrative to determine the selection rules

Table 1. Factor group analysis of BaTiO, in its cubic phase

E 6C4 3 C i 8C3 6Cz

i 6S4 3uh 8Ss 6 r d

JOURNAL OF RAMAN SPECTROSCOPY, VOL. 10, 1981 259

D. L. ROUSSEAU, R. P. BAUMAN AND S. P. S. PORT0

The method of counting invariant oxygen atoms is less

coordinates describing the librational and translational

f , , - 5 f o ( v 3 ,v4, trans, lib, acoustic)

Figure 3. Correlation table f o r CaW04. The translational (trans)

@ Heyden & Son Ltd, 1981

NORMAL MODE DETERMINATION IN CRYSTALS

Figure 4. (a) Body-centered unit cell (non-primitive) of calcium

not be readily predicted. In many instances such splitting

Tea= Tw= 2A, + 2Bg + 2Eg + 2Eu.

ro4= 6Ag + 6A, + 6 4 + 6B, + 6Eg+ 615,.

@ Heyden & Son Ltd, 1981

D. L. ROUSSEAU. R. P. BAUMAN AND S. P. S. PORT0

If selection rules are to be determined for a crystal

11. D. M.Adams and D. C. Newton, J. Chem. SOC.A 1970,2822.

Received 29 August 1980

Ordering within each set of tables

Point Group symbo s

NORMAL MODE DETERMINATION IN CRYSTALS

Tables A. All sites for each of the 32 crystallographic point groups

@ Heyden & Son Ltd, 1981

JOURNAL OF RAMAN SPECTROSCOPY, VOL. 10, 1981 263

ALL SITES FOR EACH POINT GROUP