MOLSTR 10511

Journal of Molecular Structure 511–512 (1999) 69–75

www.elsevier.nl/locate/molstruc

Infrared and Raman spectroscopy in inorganic solids research q

H.D. Lutz*, H. Haeuseler
Universität Siegen, Anorganische Chemie I, D-57068 Siegen, Germany
Received 19 August 1998; accepted 30 September 1998

Abstract
Application of infrared and Raman spectroscopy in solid state chemistry, as far in use at present, is recalled. Interpretation of
the observed spectra with respect to structure and bonding of the respective compound is discussed. The main topics are
distortion of molecular units, crystal-matrix studies, band broadening and splitting, vibrational coupling phenomena, charac-
teristic frequencies, bond strength, etc. q 1999 Elsevier Science B.V. All rights reserved.
Keywords: Infrared spectroscopy; Raman spectroscopy; Inorganic solids; Structure; Bonding; Matrix spectroscopy; Vibrational coupling
phenomena

1. Introduction using sophisticated force-constant calculations.

Recording and assigning infrared and Raman spectra
Infrared and Raman spectroscopy are now, as as an end in itself are not very straightforward. Eluci-
before, a very valuable tool for research in inorganic dating special structural and bonding features,
solid state chemistry. Infrared and Raman spectra can physical properties, etc., however, are very important
be used for simple, rapidly working phase analyses, in in solid state vibrational spectroscopy.
a similar way as performed by X-ray powder photo- This article is divided into five sections:
graphs, as well as for sophisticated studies of structure
1. internal vibrations of isolated molecules,
and bonding. This article (see also [1]) deals with the
2. spectra of crystalline and amorphous solids,
interpretation of infrared and Raman spectra of inor-
3. vibrational coupling phenomena,
ganic solids, as far as possible, without detailed theo-
4. crystal matrix spectroscopy, and
retical calculations.
5. structure and bonding.
However, there are some restrictions. Thus, vibra-
tional spectra of solids are not suitable for determining The main attention is directed to that spectroscopic
the complete crystal structure of a compound. In most information, which is important for experimental
cases it is impossible to assign and to interpret all chemists.
observed bands, in particular because the real nature
of the various normal modes can only be established
2. Internal vibrations of isolated molecules
* Corresponding author. Tel.: 1 49-271-740-4217; fax: 1 49-
271-740-2555.
q
Dedicated to Professor B. Krebs on the occasion of his 60th
In the last seven decades, the vibrational spectra of
birthday. free molecules in all the gas phase, solution, and cryo-
E-mail address: lutz@chemie.uni-siegen.d400.de (H.D. Lutz) genic matrices were thoroughly studied with respect
0022-2860/99/$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
PII: S0022-286 0(98)00630-9
70 H.D. Lutz, H. Haeuseler / Journal of Molecular Structure 511–512 (1999) 69–75

Table 1 ions are much stronger than the Br–O bonds of BrO32
XO stretching modes (cm 21) of pyramidal XO3x2 and tetrahedral ions. The same can be established for the Cl–O and
XO4x2ions [6]
B–F bonds in ClO42 and BF42 ions, respectively.
n 1 (n XO sym) n 3 (n XO asym) n XO (mean value) a

PO432 938 1017 997

SO422 983 1105 1063
3. Spectra of crystalline and amorphous solids
ClO42 928 1119 1071
BF42 777 1070 997 In solid state, the vibrational spectra of molecular
ClO32 939 971 960 or ionic units are changed with respect to the gas or
BrO32 797 797 797 liquid phase. Bands may be
IO32 796 745 762
1. shifted to higher or lower wavenumbers,
a
Calculated by using the formula nXO ˆ ‰…n21 1 2n23 †=3Š1=2 :
2. increased in halfwidth (in part strongly),
3. split into two or more components, and further
4. additional bands, not allowed in the case of free
to information on their structure and bonding. Thus,
molecules, may be observed.
the structure of most inorganic molecules and mole-
cular ions were established by infrared and Raman Thus, the various normal modes of polyatomic
spectroscopic methods via group theoretical treat- units are mostly shifted to higher or lower frequen-
ment, especially in the 1930 until the 1960 of this cies. For these frequency shifts, the following reasons
century. Using the observed intensities of the respec- are possible:
tive bands bond charges (from infrared data) and
1. Weakening of the intramolecular (or intraionic)
derived bond charges (from Raman data) were deter-
bonds owing to intermolecular (interionic) bonding
mined, which yield valuable information on the
features, which result in a redshift of the bands as a
polarity of the respective bonds and the electronic
consequence of the decrease of the respective
structure of the molecules [2–5].
internal force constants,
Interpretation of the obtained infrared and Raman
2. change of the polarity or the nature of the intramo-
spectra, however, must be done with great care. Many
lecular bonds, which may lead to a blueshift or a
spectroscopists like to rush to conclusions on the basis
redshift of the normal modes,
of poor spectra and, hence, they bring molecular spec-
3. repulsive forces of the lattice, which cause only
troscopy into discredit for many other scientists.
small blueshift,
Nevertheless, it is possible to gain a lot of informa-
4. intermolecular coupling of normal modes which
tion, even from simple infrared and Raman spectra.
can produce both redshifts and blueshifts, and
Some examples are given in the following.
5. increase of the anharmonicity of vibrations, espe-
Thus, the different strength of X–O bonds, for
cially in the case of XH stretching modes of
instance, of pyramidal and tetrahedral oxoanions
hydrogen bonded entities, which strongly enlarges
XO3x2 and XO4x2 can directly be established from the
the redshift as it is because of the weakening of the
spectra without any theoretical calculations (see Table
XH bond [7,8].
1). Keeping in mind the different masses of X, it can
immediately be revealed that the I–O bonds of IO32 The redshift of internal modes of molecules or ions
in a solid environment owing to a decrease of the
Table 2 intramolecular force constants normally does not
ClO stretching modes (cm 21) and unit-cell volumes (10 6 pm 3) of exceed 20–40 cm 21. Intermolecular bonds, which
baryte-type perchlorates [9,10] weaken the intramolecular bonds, may be, for
KClO4 RbClO4 CsClO4 TlClO4 example, owing to some covalency in the metal–
oxygen interactions of oxoanions in anhydrous salts.
n1 942 940 938 924 Thus, the ClO stretching modes of TlClO4 are signifi-
n3 1121 1119 1113 1086
cantly smaller than those of isostructural alkali metal
Unit cell volume 364 400 458 408
perchlorates (see Table 2). This must be ascribed to
 H.D. Lutz, H. Haeuseler / Journal of Molecular Structure 511–512 (1999) 69–75 71

the more covalent Tl–O bonds compared to M–O of n 1 in the infrared spectra of such compounds is a
bonds of the alkali metal perchlorates [9]. measure of the extent of distortion of the ions at the
The halfwidths of molecular modes in solid lower symmetric lattice site as compared to that of the
compounds may be only a few wave numbers free ion [9,11]. Prediction of site group splitting can
resulting in very sharp bands, especially with the be easily established by group theoretical treatment,
Raman experiment. Contrarily, there are very broad especially the correlation method [12], of the mole-
spectral features possible, especially in the case of cular unit using point group and symmetry elements
infrared spectra. The reasons of band broadening in of the respective lattice site.
solid state are
1. TO/LO splitting of IR allowed bands,
2. loss of translational symmetry in the case of both
4. Vibrational coupling phenomena
amorphous compounds and static or dynamic
disorder phenomena, and
There are various mixing or coupling phenomena
3. anharmonic coupling of low-frequency modes, as
of molecular vibrations, even in the case of molecules
it is expressively pronounced in the presence of
in the gas phase, in particular, in solid state spectro-
hydrogen bonds.
scopy. Each kind of vibrational coupling can only
The number of molecular modes mostly increases occur if the vibrations or hypothetical vibrations
on going from the gaseous or liquid state to the solid involved belong to the same species. The resulting
one. This well known fact may be caused by coupled modes, however, do not have to belong to
the same species. The various coupling features may
1. the presence of chemically identical but crystallo-
be separated into
graphically different molecules or ions in the struc-
ture linked by bonds of different strength, e.g. 1. intramolecular vibrational coupling,
crystallographically different crystal H2O mole- 2. homoeotype intermolecular vibrational coupling,
cules in salt hydrates [8], 3. heterotype intermolecular vibrational coupling,
2. the lower symmetry at the respective lattice site 4. intercellular intermolecular vibrational coupling,
compared to that of the free molecule (site group 5. coupling of anharmonic vibrations, and
splitting), 6. coupling of lattice vibrations.
3. dynamical coupling of the vibrations of adjacent
The occurrence of all of them gives valuable infor-
molecules (unit-cell group splitting),
mation on the respective force fields and the intermo-
4. TO/LO splitting of Raman bands in the case of
lecular interactions of the compounds under
compounds with acentric space groups,
investigation. For studying bonding features or the
5. disorder of molecules or molecular ions over two
static lattice potential at special lattice sites coupling
or more different lattice sites, and
phenomena are obstructive and should be avoided, for
6. two (or three)-mode behaviour of modes in the
example, by matrix methods, especially by the isotope
case of both solid solutions (mixed crystals) and
dilution technique.
compounds containing different isotopes.
A special kind of intramolecular coupling in solid
Lower site symmetry of molecular units in the state is the coupling of librational modes with trans-
lattice may lift the degeneracy of degenerate normal lational (or much less frequently internal) vibrations
modes as well as make allowance of (in the case of of a molecular unit [8,9,13]. Strong coupling of libra-
free molecules) silent modes in the IR or Raman tions and translational modes, which is very common
spectra. Thus, in the case of tetrahedral XO4n2 ions, for H2O molecules in solid hydrates [8] and OH 2 ions
lowering the Td symmetry results in splitting of the in hydroxides [13,14], results in strongly mixed
threefold degenerate XO stretching and XO4 bending modes, which display isotopic shifts in between of
modes n 3 and n 4 into three components as well as in those of librational, e.g. 1.3–1.4 for H2O/D2O [8],
the allowance of the in Td symmetry IR forbidden XO4 and translational vibrations (H2O/D2O , 1.06 [8]).
breathing mode n 1 in the IR experiment. The intensity In addition, more modes than predicted by group
72 H.D. Lutz, H. Haeuseler / Journal of Molecular Structure 511–512 (1999) 69–75

theory may have libration like isotopic shifts as, for tallographically different but chemically equal mole-
example, in the case of brucite-type M(OH)2 [14]. cules, e.g. between crystallographically different H2O
Internal modes of crystallographically and chemi- molecules in solid hydrates [18], is possible under the
cally equal molecular units in a crystal couple dyna- same conditions and restrictions as normal intermole-
mically to so-called unit-cell (or factor) group modes cular coupling phenomena. Hence, it is likewise
(homoeotype intermolecular coupling). This means common but not easily undoubtedly proved. Example
that the respective vibrations of the molecular units are the MgSO3·3H2O-type compounds, in the case of
in the primitive unit cell are in phase or in anti-phase, which some OH stretches are shifted by . 100 cm 21
etc. For group theoretical treatment of the unit-cell owing to heterotype intermolecular coupling [18]. For
group splitting, we recommend the tabular method this reason, the frequencies of the water bands of neat
[15]. The frequencies of the various unit-cell group compounds are much less suitable for studying struc-
modes differ more or less depending on the extent of ture and bonding effects than the respective uncoupled
the intermolecular vibrational coupling. This is modes observed in isotopically dilute samples.
caused, mainly, by two physical processes, viz. elec- Intermolecular vibrational coupling phenomena are
trostatic dipole–dipole interactions [12] and repulsion not restricted to the entities inside the primitive unit
effects of entities coming too close to another during cell. If the general conditions for intermolecular
the atomic motion [12]. Unit-cell group splitting, coupling of molecular modes are fulfilled, vibrations
which can be neglected for molecular units more of molecules or ions of adjacent primitive cells of the
distant than 400 pm [16], ranges from a very few to structure may also be dynamically coupled and
. 250 cm 21, for example, in the case of the librational thereby shifted to higher or lower wavenumbers
modes of OH 2 ions in brucite-type compounds compared to those of free molecules. In the case of
[16,17]. The mean value of the wavenumbers of the strong intercellular vibrational coupling, the mean
various unit-cell group modes of a molecular vibra- value of the various unit-cell group mode frequencies
tion normally resembles the wavenumber of the vibra- differ from that of the respective uncoupled vibra-
tion of the respective isolated molecular unit. The tions. An example for intercellular molecular
latter can be recorded via matrix isolation techniques. coupling is CaCO3 aragonite, in the case of which
On comparing with data of gas phase, liquids, or solu- the mean value of the unit-cell group modes of the
tions, however, band shifts owing to the static field at out-of-plane bending vibration n 2 of 12CO322 ions
the respective lattice site have also to be considered. differ from that of uncoupled modes in isotopically
Intermolecular vibrational coupling can also occur diluted samples by . 40 cm 21 [21].
between crystallographically or chemically different A serious problem of vibrational spectroscopy of
molecules or ions in the primitive unit cell [17–19]. solid compounds is the coupling (mixing) of the
Heterotype intermolecular coupling is, for instance, various lattice (translational) modes. The coupling
very common between OX stretching modes of oxoa- of the vibrations of different structural units in a
nions XOnx2 and librations of hydrate H2O molecules solid, which is mostly, at least very often, underesti-
[19,20]. In the case of salt hydrates, therefore the mated, prevents the concept of characteristic frequen-
frequencies of the OX stretching vibrations of these cies in inorganic solid state spectroscopy with the
ions may differ by up to 30 cm 21 between the spectra exception of some favourable cases. For instance, in
of protonated and deuterated samples [19]. In order to the older literature, the infrared bands of spinel-type
record the true frequencies of the XO stretching modes compounds, i.e. the four IR allowed lattices modes,
the spectra of deuterated samples should be examined are separated into those belonging to the tetrahedral
because the bands owing to D2O librations are shifted structural unit and those caused by the octahedral one
to lower wavenumbers as compared to the H2O ones [22]. This is not true, as it was already claimed in the
and, hence, coupling with the XO stretches is negli- 1960s [23]. All atoms of the spinel structure and
gible. Contrarily, true XOnx2 bending mode frequen- mostly all bonds contribute more or less to all IR
cies may be better observed in the spectra of allowed phonon modes [24]. For assignment and
protonated compounds [20]. interpretation of the vibrational spectra of solids,
Heterotype intermolecular coupling between crys- which contain no molecular units, utmost caution is
 H.D. Lutz, H. Haeuseler / Journal of Molecular Structure 511–512 (1999) 69–75 73

advisable. Coupling of lattice modes, all of which do matrix display the normal modes of this unit with
not much differ in frequency, can only be ruled out if respect to the symmetry of the respective site (site
they belong to different species. In this manner, symmetry). This information may be used in order
Raman spectra are frequently more convenient than to both
infrared spectra. In the case of the, in maximum of the
1. study the molecular structure (and its change) of
cases, three IR allowed species, mostly all atoms of
the incorporated entity depending on the site
the structure contribute to the respective normal vibra-
symmetry and
tions whereas in the case of Raman allowed species,
2. examine the lattice potential of the host crystal at
very often only a part of the atoms present in the
the respective site, as shown by the extent of distor-
structure are involved in the respective phonon
tion of the matrix isolated unit [25,29].
modes.
The distortion of the incorporated molecules or ions
at the various lattice sites (as compared to the free
5. Crystal matrix spectroscopy entities in solution or in the gas or liquid phase) thus
established is called energetic distortion as distin-
In the case of substitutional or interstitional incor- guished from geometric distortion, i.e. change of
poration of small amounts of foreign atoms or ions distances and angles as revealed by structural studies
into a crystal lattice, the vibrations of such matrix [29]. Assignment of the various modes of matrix
isolated entities may be examined without any distur- isolated entities can be performed by Raman (and
bance by intermolecular coupling effects. Only the infrared) single-crystal experiments via the oriented
symmetry and the static potential at the respective gas model [30,31]. In the oriented gas model, the
lattice site can influence allowance and frequencies (Raman) intensities of the normal vibrations of free
of the respective modes. Thus, vice versa the IR and molecular units are connected to those recorded with
Raman spectra of matrix isolated ions or molecules single-crystal experiments by the equation Iij / (a *) 2
reflect symmetry and lattice potential of the respective where a * is the projection of the molecule scattering
lattice site very precisely [8,25,26]. There are several tensor on the crystallographic co-ordinate system. In
variants of crystal matrix spectroscopy: this manner, change and interdependence of intramo-
lecular coupling of the molecular modes because of
1. the isotope dilution technique,
symmetry and gradient of the lattice potential at the
2. solid solution spectroscopy, and
respective lattice site can be examined. This, for
3. the double-matrix spectroscopy [27].
example, was shown for the halate ions ClO32,
The isotope dilution technique, i.e. substitution of BrO32, and IO32 in various halate host lattices
an atom of a compound by a small amount, e.g. 5%– [25,31]. In the case of these ions with C3v symmetry
10%, of a heavier or a lighter isotope, is a very in solution intramolecular coupling of the stretching
frequently used procedure, especially that of H/D modes differ strongly [6]. Thus, the symmetric and
isotopic exchange [8]. Infrared and Raman spectra asymmetric stretches n 1 and n 3 range as n 3 . n 1 for
of the so called isotopically dilute samples of ClO32, n 3 ˆ n 1 for BrO32 [6], and n 3 , n 1 for IO32
hydrogen compounds, i.e. those deuterated for 5%– whereas on lattice sites with potentials strongly
10% or 90%–95%, are a very valuable tool in deviating from C3v symmetry intramolecular coupling
hydrogen bonds research of solid hydrates, hydro- of the three XO stretches is dropped [31].
xides, and various organic materials [8,13,28]. Thus,
the OD stretching frequencies recorded from the
spectra of such samples reflect the strength of the 6. Structure and bonding
hydrogen bonds present more precisely and are
more trustworthy than any other theoretical or experi- Infrared and Raman spectra as well as inelastic
mental procedures. neutron scattering experiments display very inter-
Infrared and Raman spectra of matrix isolated esting information on structure, bonding, and various
molecules or ions on lattice sites of a crystalline physical properties of solid materials. Thus, the force
74 H.D. Lutz, H. Haeuseler / Journal of Molecular Structure 511–512 (1999) 69–75

constants derivable from the observed band frequen- XOnx2, HmXOnx2, X2Onx2, etc. can be clearly distin-
cies are one of the very few observables of the guished [38]. This is possible on the basis of the
strength of localised bonds in solid compounds. The respective XO stretching modes, which strongly differ
effective dynamical charges of the various atoms of a with respect to the co-ordination polyhedron of the
structure, which are obtainable from the TO/LO split- non-metal atom X and to bridging and terminal XO
ting of the phonon modes as well as from the results of groups [6,39]. In the case of selenites, for example,
lattice dynamical calculations, reveal valuable infor- the SeO stretches of SeO322 ions are observed at 760–
mation on the ionicity of the compounds under inves- 875 (n s) and at 680–775 cm 21 (n as), those of HSeO32
tigation. Though vibrational spectroscopy is no and S2O522 in the ranges 805–900 (n s), 700–830 (n as),
technique for structural research, in particular, as and 600–670 cm 21 (n SeOH) and 800–920 (n s,t. (ˆterm-
compared to the various diffraction methods, in inal), 730–840 (n as,t.), 540–610 (n s,b.(ˆbridge)), 515–
favourable cases, however, valuable information can 550 cm 21 (n as,b.), respectively [40].
be obtained. For the various physical properties, as Of course, vibrational spectroscopy is no method
plasma resonance frequencies (concentration of free for crystal structure determination. In some special
carriers), dielectric constants, etc., which can be cases, however, it may be a valuable tool to help in
established via infrared and Raman spectroscopic its elucidation. Such special cases are
experiments, is referred to the respective text books
1. distinction of centrosymmetric and acentric crystal
[32,33].
structures,
In some favourable cases, the wavenumbers of the
2. prediction of co-ordination numbers and oxidation
observed infrared or Raman bands are a direct
states of metal ions in halides, oxides, chalcogen-
measure of the strength of the respective bond. This
ides, etc.,
is especially true for XH and XD stretching modes of
3. hints to the number of atoms in the primitive unit
matrix isolated entities because in the case of these
cell, and
modes both intramolecular and intermolecular
4. indication of possible isotypism.
coupling phenomena can be neglected. An, even
though crude, measure of the bond strength in solids The method of characteristic frequencies, which was
are mass weighted “central frequencies” (Plendl very successful in the classical molecular spectro-
frequencies), i.e. the intensity weighted mean of the scopy, must be studied with great caution for typical
bands of normal infrared spectra of polycrystalline solid compounds without distinct molecular units as
samples [34,35]. already discussed before.
Hence, vibrational spectroscopy was employed to In the case of compounds with metal ions, which
hydrogen bond research for a long time. Thus, the OD are able to form different co-ordination polyhedra as,
stretches of solid hydrates and hydroxides, especially for example, the various polymorphs of MnS and
those observed in the spectra of isotopically dilute indium selenide In2Se3 [41], ternary nickel chlorides
samples, correlate with the H…X hydrogen bond [42,43], etc., the co-ordination polyhedra formed can
distances known for a long time [8,13]. Very recently, be recognised from the wavenumbers of the highest
nearly linear correlation of the OD stretches with the energy lattice modes. They are shifted to higher wave-
intramolecular O–H distances were established [36], numbers with decreasing co-ordination number [39].
which can be used in order to estimate intramolecular The number of modes, i.e. that of the vibrational
O–H distances more accurately than by neutron fundamentals, observed in the infrared and Raman
diffraction methods. spectra of solids cannot exceed that predicted by the
In order to recognise and interpret the structures of formula 3n–3 with n the number of atoms in the
molecular units in solid state, vibrational spectro- primitive unit cell (but remember special cases as
scopy is as powerful as in the case of free molecules. Fermi resonance phenomena, disorder, mixed crys-
In addition, a lot of information on intermolecular tals, etc.). Thus, a large number of bands in both
interactions in the solid state is revealed. Thus, for Raman and infrared spectra is an unequivocal indica-
example, metaperiodates and the various orthoperio- tion that the primitive unit-cell is relatively large with
dates [37] or generally salts containing oxoanions as respect to the number of atoms or formula units
 H.D. Lutz, H. Haeuseler / Journal of Molecular Structure 511–512 (1999) 69–75 75

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