Journal of Molecular Structure 744–747 (2005) 79–92

www.elsevier.com/locate/molstruc

Minerals from Macedonia XIII: Vibrational spectra of some commonly

appearing nesosilicate minerals
Petre Makreski*, Gligor Jovanovski, Silvana Stojančeska
Institute of Chemistry, Faculty of Science, Ss. Cyril and Methodius University, Arhimedova 5, P.O. Box 162, 1001 Skopje, Republic of Macedonia
Received 6 September 2004; accepted 4 October 2004
Available online 17 February 2005

Abstract
The vibrational (infrared and Raman) spectra of seven common nesosilicate minerals [almandine, Fe3Al2(SiO4)3; spessartine,
Mn3Al2(SiO4)3; zircon, ZrSiO4; titanite, CaTiOSiO4; olivine, (Mg,Fe)2SiO4; kyanite, Al2OSiO4 and staurolite, Fe2Al9O6(SiO4)4(OH)2] in
the region from 1200 to 370 cmK1 (infrared, for staurolite from 3750 to 3250 cmK1, as well) and from 1200 to 100 cmK1 (Raman) are studied.
The observed spectral behavior is discussed in terms of the structural characteristics of orthosilicates (nesosilicates) where no oxygen atoms are
shared between the adjacent SiO4 tetrahedra. In spite of some differences, in general, rather expressed similarity among the infrared spectra of
the minerals are observed in the region below 1200 cmK1, mainly due to their common structural characteristics. The similarity is especially
expressed in the case of the isomorphous almandine and spessartine garnets, which form solid solution. Except staurolite, all mentioned
minerals are nominally anhydrous and do not contain OH groups. The similarity between the Raman spectra of the studied minerals is less
expressed compared to the IR analogues. The vibrational spectra of the studied mineral samples are compared with the corresponding literature
data for the analogous mineral species originating all over the world and used for mineral identification.
q 2004 Published by Elsevier B.V.

Keywords: Vibrational; Infrared; Raman; Spectra; Nesosilicate; Orthosilicate; Minerals; Almandine; Spessartime; Zircon; Titanite; Olivine; Kyanite;
Staurolite

1. Introduction of the infrared and Raman spectral study of the collected

Working on the systematic collection, identification and
characterization of the minerals originating from Macedonia,
we have studied a significant number of carbonate [1,2],
sulfate [3], sulfide [4,5] and oxide [6] mineral species from
various localities using infrared and Raman vibrational
spectroscopy as well as the X-ray powder diffraction. The
research has predominantly been focused on mineral identi-
fication and characterization, recently being spread to the
determination of the content of trace elements, i.e. elements
which do not take part in the regular mineral composition [2,7,
8]. Thus, in the process of mineral separation, purification and
characterization, significant number of non-silicate minerals
has been systematically investigated.
Recently, the study was extended to the most abundant
group of silicate minerals [9]. Here are presented the results
* Corresponding author. Tel.: C389 91 117055; fax: C389 91 226865.
E-mail address: petremak@iunona.pmf.ukim.edu.mk (P. Makreski).
0022-2860/$ - see front matter q 2004 Published by Elsevier B.V.
doi:10.1016/j.molstruc.2004.10.025
nesosilicate minerals originating from Macedonia as well as
their separation, purification and identification.
Identification was based on the comparison of our IR
results with the corresponding literature data for the
analogous mineral species originating all over the world.
Several studies have been undertaken to study infrared spectra
of almandine [10–14], spessartine [11–14], zircon [13,15–
17], titanite [13], olivine [11,13,18,19], kyanite [13,20,21],
staurolite [13,22], on single and/or microcrystalline samples.
Having in mind that the studied minerals are natural,
sometimes the spectral differences are expected to appear
making the identification not always a straightforward task.
Also, Raman spectra of almandine [12,14,23–26], spessartine
[14,23–25], zircon [23,26], titanite [23,27], olivine [23,28],
and kyanite [29] are additionally used for mineral character-
ization. The Raman data for staurolite, to the best of our
knowledge, have not been found in the literature.
There are at least two reasons to study these minerals: (i)
all minerals are orthosilicates and show structural
80 P. Makreski et al. / Journal of Molecular Structure 744–747 (2005) 79–92
similarities; (ii) no survey has been undertaken on
systematic study of the nesosilicates from Macedonia.
Therefore, the aim of this work is to compile our
vibrational data with the literature data and to present a
summed analysis of the infrared and Raman spectra of these
seven minerals based mainly on their structural
characteristics.
2. Experimental
2.1. Samples
The studied nesosilicates were collected from various
localities: almandine (Pelagon), spessartine (Lojane), zircon
(Kozjak), titanite (Dunje), olivine (Ržanovo), kyanite and
staurolite (Štavica). The investigated minerals were care-
fully picked up under a microscope from the ore samples
and than powdered.
2.2. Instrumentation
The Perkin–Elmer FTIR system 2000 interferometer was
employed for recording the spectra using the KBr pellet
method.
The Raman spectra of the studied samples were recorded
on two instruments: Bruker FT Raman model 106/S
connected to FTIR interferometer Equinox 55 with
1064 nm line of Nd-YAG frequency laser, and on Renishaw
micro-Raman 1000 spectrometer equipped with Peltier
cooled CCD camera and Leica microscope for sample
illumination with 50! magnification and numerical
aperture of 0.75. The Raman effect was excited using the
514 nm line of an air cooled ArC laser by Melles Griot.
The measurements were carried out at a room tempera-
ture and spectral data were analyzed with the GRAMS/32
software package.
3. Crystallographic data
The main feature of the nesosilicate minerals is that SiO4
tetrahedra are not bonded to other tetrahedra (no oxygen
anions are shared between the adjacent tetrahedra). There-
fore, net negative charge of the isolated silicon tetrahedra is
neutralized by bonding with other cations such as Mg2C,
Fe2C, Al3C etc.
The most important crystallographic parameters for the
studied minerals are given in Table 1. In order to support the
assignment of the bands in the Raman and far infrared
spectra of these minerals, the structural differences and/or
similarities between the studied nesosilicates are briefly
emphasized and discussed below.
(a) The cation (Al3C, Mg2C, Fe2C, Zr4C) coordination
spheres in the structures of olivine, almandine,
spessartine and zircon consists of oxygens belonging to
the silicon tetrahedra, whereas coordination spheres of
the cations (Al3C, Fe2C, Ca2C, Ti4C) in the kyanite,
staurolite and titanite structures, in addition to the SiO4
oxygens, are also coordinated by O and/or OH that are
not part of the silicon tetrahedra.
(b) Almandine and spessartine are isomorphous and
crystallize in the cubic Ia3d space group. Considering
the isomorphous substitution, both minerals form ideal
solid solutions whose cell parameters should be simply
dependent on the chemical composition of the mixture.
(c) Aluminum octahedra in the structure of kyanite are
linked laterally through Si and Al and are very similar
with the Al octahedral chains in the structure of
staurolite, whereas both iron and silicon occupy
tetrahedral sites.
(d) Staurolite is the only studied representative which is not
nominally anhydridous and contains OH groups.
4. Results and discussion
4.1. Infrared and Raman spectral study
4.1.1. Almandine, Fe3Al2(SiO4)3 and spessartine,
Mn3Al2(SiO4)3
For minerals with complex structure, the selection of a
unique polyatomic vibrational group to whose the observed
vibrational (infrared and Raman) bands of the studied
polycrystalline sample could be attributed is not a
straightforward task and assigning the normal modes to
specific atomic motions is not always very informative.
However, the SiO4 tetrahedra in the garnet structures are
nearly independent and Si–O bonds are considered much
stronger than 6- and 8-fold cation bondings to the SiO4
tetrahedra. Thus, the interpretation of the infrared (and
Raman) spectra is based on the existence of the SiO4
tetrahedra as the main vibrational units.
In order to relate the vibrational and the crystallographic
characteristics of the isomorphous minerals almandine and
spessartine (Section 3), their powder IR absorption spectra
in the wavenumber range 1200–370 cmK1 (Fig. 1) as well
as their Raman spectra in the region from 1100 to 100 cmK1
(Fig. 2) are studied together. Although the strong intensity
patterns, typical for garnets [14] are observed, it should be
pointed out that the peaks in the presented IR spectra are
sharper and better resolved than the corresponding spectra
previously recorded by Moore et al. [12]. According to the
selection rules, 17 IR active bands are predicted (and found)
[12], whereas the assignment of the bands by Hofmeister
and Chopelas [14] has been considered in the IR reflectance
study. As seen from Fig. 1, two well-defined spectral
regions are observed for both spectra.
The first region includes bands above 800 cmK1 arising
from the high-energy modes. In this region, one shoulder
 P. Makreski et al. / Journal of Molecular Structure 744–747 (2005) 79–92 81

Table 1
Crystallographic data for the studied nesosilicate minerals [30]

Mineral
Almandine, Fe3Al2(SiO4)3
Spessartine, Mn3Al2
(SiO4)3
Forsteritea, Mg2SiO4
Fayalitea, Fe2SiO4
Zircon, ZrSiO4
Titanite, CaTiOSiO4
Kyanite, Al2OSiO4
Staurolite, Fe2Al9O6
(SiO4)4(OH)2
a
Both mineral are end-members from olivine (Mg,Fe)2SiO4.
Crystal system Space group Z Unit cell vol (Å3) Structural type
Cubic 
Ia3d 8 1533.2 Isolated silicon tetrahedra bonded laterally through
cations in 6- and 8-fold coordination. Si tetrahedra
and Al octahedra share single O anions to form chains
parallel to each of the a-axis. The spaces between
these chains are distorted 8-fold sites occupied by the
Fe cations
Cubic 
Ia3d 8 1565.7 Isolated silicon tetrahedra bonded laterally through
cations in 6- and 8-fold coordination. Si tetrahedra
and Al octahedra share single O anions to form chains
parallel to each of the a-axis. The spaces between
these chains are distorted 8-fold sites occupied by the
Mn cations
Orthorhombic Pbnm 4 289.58 Distorted hexagonally close packed array of oxygen
with 1/8 of the tetrahedral sites occupied with Si,
whereas one half of the octahedral sites are occupied
by Mg cations
Orthorhombic Pbnm 4 307.42 Distorted hexagonally close packed array of oxygen
with 1/8 of the tetrahedral sites occupied with Si,
whereas one half of the octahedral sites are occupied
by Fe cations
Tetragonal I41/amd 4 260.8 Relatively large Zr cation fit comfortably in 8-fold
coordination, The structure can be considered to
consist of chains parallel to c in which Si tetrahedra
alternate with Zr in 8-fold coordination
Monoclinic P21/a 4 370.23 Structure consists of kinked chains of corner-sharing
TiO8K6 octahedra that run parallel to [110]. These
chains are held together laterally through Si in
tetrahedral coordination and Ca in irregular 7-fold
coordination
Triclinic P1 4 293.72 Edge-sharing chains of Al octahedra that are linked
laterally through Si and Al. Half the Al is distributed
in the octahedral sites to form zig-zag chains parallel
to the c-axis and the other half in octahedra that form
straight chains. Silicon in tetrahedral coordination
links both chains together
Monoclinic C2/m 1 739.94 The Al occupies octahedral sites and both Fe and Si
occupy tetrahedral sites. The cations are distributed so
that Al-bearing octahedra extend in edge-sharing
chains parallel to c with additional Al octahedra and
Si and Fe tetrahedra linking between chains

and three strong bands which appear at 998, 967, 901, 877 in
almandine and 976, 944, 881, 859 cmK1 in spessartine
spectrum are observed and are in accordance with the
corresponding literature data (Tables 2 and 3). These bands
are assigned as n3 modes from the main vibrational units—
the SiO4 tetrahedra [14]. Additional weak band is also
registered around 1090 cmK1 in the spectrum of almandine
and (even better developed) spessartine. Band at the same
frequency is also registered in the synthetic almandine IR
spectrum studied by Boffa et al. [10] and also by Nicodom
[13] in the spectra of both natural minerals, but not by other
authors (Fig. 1, Tables 2 and 3). It might be due to
the presence of the small content of the same impurities in
the samples.
The second well-developed region merges the peaks
from the low energy modes from 700 to 400 cmK1 (Tables 2
and 3). The lowest band at around 450 cmK1 observed in
the spectra of both minerals corresponds well with the
literature data and is prescribed to the n2 mode of the SiO4
tetrahedra. The highest frequency three bands in this region
of the spectrum of almandine (at 640, 571 and 530 cmK1)
are also in very good consistence with the literature data
(Table 2) being due to the n4 modes of the SiO4 tetrahedra
[14]. Similar spectral behavior, manifested by the appear-
ance of three bands with somewhat lower frequencies
(the shifting being 10, 13 and 19 cmK1, respectively) in
650–500 cmK1 region of spessartine spectrum is observed
(Tables 2 and 3). Here, it should be pointed out that similar
decreasing trend for the n3 frequency modes of the
spessartine spectrum compared to the corresponding mode
in the spectrum of almandine has been registered. It means
that the vibrational frequencies of the garnet mineral with
the smaller unit cell volume (Table 1) are, in general,
higher. These observations are consistent with the trends in
82 P. Makreski et al. / Journal of Molecular Structure 744–747 (2005) 79–92
Fig. 1. Infrared spectra of almandine (a) and spessartine (b).
M2C–O bond length or M2C-cation mass (MZFe and Mn)
in these minerals [14]. The comparison of band frequencies
in the studied IR absorption spectra of both garnet minerals
with those in the reflectance spectra [14] shows that they are
Fig. 2. Micro-Raman spectra of almandine (a,b) excited with 1064 and
514 nm lines, respectively. Micro-Raman spectrum of spessartine (c)
obtained with 1064 nm line.
much closer to the TO mode frequencies, especially in the
case of the spessartine spectrum.
According to the studies surveyed in the full range IR
spectra [12,14], seven weak to medium bands are registered
below 400 cmK1. Because of the frequency restrictions,
only the highest frequency band is observed in the spectra of
both studied garnet samples at around 380 cmK1 being
assigned predominantly as SiO4 rotations (Tables 2 and 3).
Two Raman spectra of almandine recorded on different
instruments and with different excitation lines (Section 2)
are presented in Fig. 2a and b, whereas the attempt to record
the spessartine spectrum with 514 nm failed (Fig. 2c). As
seen from Fig. 2a and b, the Raman spectra of the same
almandine specimen recorded with various excitation lines
are, at some extent, similar, but also show some significant
differences (Table 4) suggesting that one should be careful
enough during their use for spectra–structure correlations as
well as for identification purposes.
The predicted number of bands in the Raman spectra of
garnets by the factor group analysis is 25 [12] and makes,
in general, the Raman spectra more complex than the
corresponding infrared spectra. As seen from Fig. 2, the
bands in the Raman spectra of both garnet minerals are
grouped in three separated regions: high energy peaks
(1050–800 cmK1), medium (650–450 cmK1) and low
frequency peaks (400–150 cmK1). The latter group bands
appearing above 200 cmK1 are assigned as rotational and
translational (or mixed) SiO4 modes, whereas the bands
below 200 cmK1 are attributed to the translation modes of
M2C (MZFe or Mn) [14].
All Raman peaks in the 650–450 cmK1 region for single
crystal of almandine mentioned in the literature [12,14,24,
26] and prescribed to the bending n2 and n4 SiO4 modes are
found at frequencies and with intensities similar to those
registered in our spectra (Table 4). Exception are the two
strongest bands at 446 and 607 cmK1 registered only in the
studied spectrum obtained with 1064 nm excitation line.
In fact, all bands observed in the Raman spectrum taken by
514 nm excitation line are present in the spectrum obtained
with the 1064 nm excitation line, where the above
mentioned two additional bands in this region appear.
Since, the 514 nm Raman spectrum shows closer similarity
with the corresponding spectrum of the isomorphous
spessartine analogue, it is more likely that some structural
changes appear during the recording of the almandine
1064 nm Raman spectrum.
The bands observed above 850 cmK1 in the Raman
spectrum of almandine are assigned as the Si–O strechings,
the strongest one at around 920 cmK1 being precisely
attributed to the symmetric stretching mode of SiO4
tetrahedra (Table 4). Although the Raman spectrum of
spessartine is of somewhat lower quality (Fig. 2c), the best
separated band is the strongest one arising from the n1 mode
of SiO4 tetrahedra observed at 901 cmK1, which is in
accordance with the literature band at 905 cmK1 [14,24]
(Table 5). Additional three weak bands appear in this region
 P. Makreski et al. / Journal of Molecular Structure 744–747 (2005) 79–92 83

Table 2
Frequencies and intensities of the bands in the powder infrared spectrum of almandine compared with the corresponding literature data

This work Nicodoma [13] Moore et al.b [12] Moenkea [11] Hofmeister and Chopelasc–e [14] Boffa et al.a,f,g [10] Assignmenth
LO TO
379 m 376 396 376 378 s SiO4 rotations
455 s 454 m 448 455 m 518 448 442 m n2
476 s 475 m 469 480 m 461 468 465 vs Al translations
530 w 530 vw 526 527 s 534 525 525 w n4
571 s 568 s 571 – 597 561 570 vs n4
640 w 640 vw 635 638 m 638 634 635 w n4
877 s 887 s 870 872 s 882 889 875 s n3
901 s 899 s 897 902 s 923 865 900 s n3
967 vs 965 s 960 970 vs 1038 952 970 vs n3
998 sh 993 sh 991 995 sh
– 1043 sh – –
1085 sh 1096 sh – 1085 sh
a
Wavenumbers are approximate because explicite numerical data are not given.
b
Additional bands are found at 116, 137, 156, 192, 237, 317 and 338 cmK1.
c
Intensities are not given.
d
IR reflectance spectrum.
e
Additional bands are found at 115, 147, 160, 205, 246, 322, 347, 422 cmK1 (LO) and 111, 137, 158, 196, 236, 318, 345, 412 cmK1 (TO).
f
Synthetic sample.
g
Additional bands are found at 116, 137, 158, 200, 237, 316 and 342 cmK1.
h
According to Hofmeister and Chopelas [14].

(at 838, 976 and 1025 cmK1) being assigned as antisym-
metric SiO4 stretching vibrations.
The 650–400 cmK1 Raman spectral region of spessartine
is characterized by the bands due to the bending SiO4
modes. All registered bands in this region are found at close
frequencies with the corresponding literature data except the
very weak band at 520 cmK1 which is absent in our
spectrum (Table 5). It is worth mentioning that the number
of the observed bands in the lower frequency region (below
350 cmK1) is twice smaller compared to the literature data
(Table 5). It seems that the literature weak peak doublets at
318 and 300, 229 and 220, 194 and 173 cmK1 [14] appear
as medium singlet bands at 294, 228 and 183 cmK1,
respectively.
The closer examination of the frequencies of the
stretching as well as the bending vibrations in the Raman
and IR spectra, respectively, are in general, consistent (e.g.
IR–Raman ‘doublets’ appear (Tables 2–5). The distinguish-
ing feature between IR and Raman spectra of garnets in the
800–650 cmK1 region is the appearance of several bands in

Table 3
Frequencies and intensities of the bands in the powder infrared spectrum of spessartine compared with the corresponding literature data

This work Nicodoma [13] Moore et al.b [12] Moenkea [11] Hofmeister and Chopelasc–e [14] Assignmentf
LO TO
384 w 379 383 380 SiO4 rotations
451 m 449 m 447 452 s 531 445 n2
471 s 470 s 470 472 s 458 461 Al translations
511 sh 513 sh 495 – 517 520 n4
558 s 560 s 565 562 s 593 558 n4
630 w 630 m 631 632 m 638 630 n4
859 s 860 s 861 870 s 912 861 n3
881 s 883 s 895 892 s 871 884 n3
944 s 944 s 949 955 vs 1030 946 n3
976 sh 978 sh 976 –
1089 w 1088 w – –
a
Wavenumbers are approximate because explicite numerical data are not given.
b
Additional bands are found at 113, 140, 165, 203, 242, 308 and 341 cmK1.
c
Intensities are not given.
d
IR reflectance spectrum.
e
Additional bands are found at 115, 150, 168, 212, 249, 320, 352, 414 cmK1 (LO) and 111, 140, 167, 203, 246, 316, 350 cmK1 (TO).
f
According to Hofmeister and Chopelas [14].
84 P. Makreski et al. / Journal of Molecular Structure 744–747 (2005) 79–92

Table 4
Frequencies of the banfds in the powder Raman spectrum of almandine compared with the corresponding literature data

This worka,b This workc Calligaro et al.d Moore et al.d,e Kolesov and Hofmeister and Griffith [23] Assignmentf
[26] [12] Geigerd [24] Chopelasd [14]
147 m – – 167 163 Fe translations
170 w 168 – 170 166 Fe translations
208 w – – – 198 SiO4 translations
218 w – – – 216 212 – Fe translations
238 w 240 w – 266 256 239 – SiO4 translations
299 vw – – – – 293 – SiO4 translations
– 318 vw – – 314 312 – SiO4 rotations
– – – – 323 326 – SiO4 translations
343 m 349 m 347 307 342 347 340 SiO4 rotations
– – – – – 355 – SiO4 rotations
371 w 372 w 370 400 370 368 – SiO4 rotations
446? vs – – – – 421 – n2
– 481 vw – 468 475 474 – n2
500 w 502 m 501 – 500 498 – n4
523 vw – – 517 – 521 – n2
555 w 559 m 557 562 556 553 – n2
570 vw 586 vw – – 581 576 – n4
607? vs – – 611 596 593 – n4
– 636 w 625 644 630 628 – n4
690 w 687 vw 683 695 – – – –
– – – 745 – – – –
801 w – – 806 – – – –
861 w 865 w 862 843 863 862 870 n3
– – – – 897 892 900 n3
917 vs 921 vs 917 890 916 910 – n1
– – – – 930 920 917 n3
1041 m 1044 m 1042 1038 1032 960 n3
a
Excitation with 1064 nm.
b
Additional very weak bands appear at 118, 142, 250, 263, 271, 286, 384, 512, 535 and 14 more in 700–1050 cmK1.
c
Excitation with 514 nm.
d
Single crystal.
e
The specimen contains 23% pyrope, Mg3Al2(SiO4)3.
f
According to Hofmeister and Chopelas [14].

the Raman spectra which are not related to the SiO4 modes,
suggesting that Raman spectra are sensitive to the presence
of non-silicate tetrahedra.
4.1.2. Zircon, ZrSiO4
The infrared spectrum of powdered zircon (Fig. 3a)
shows intense and mainly well-resolved bands. Here, the
band assignment is again based on the concept of group
frequencies of the SiO4 tetrahedra as the main vibrational
units in the structure. Due to the degeneracy in the crystal,
the possible nine internal degrees of freedom of isolated
SiO4 anion are reduced to four modes, n1, n2, n3 and n4. Also,
the Zr–O forces modify the vibration of the tetrahedron and
enforce mixing of internal bending vibrations with rotations
and translations [31]. However, the three highest frequency
bands in the IR spectrum at 1014, 979 and 898 cmK1 are
assigned as n3 modes since n1 mode is infrared inactive
(SiO4 lies on D2d site) (Table 6). It is well known that in the
case of distortion of the tetrahedral symmetry as a result of
the force field due to the cation, a separation of the
components of n2 and n4 by nearly 200 cmK1 is expected
[31]. Thus, going toward lower frequencies, no doubt that
the intensive bands observed at 611 and 434 cmK1 are due
to n4 mode, whereas the shoulder at 450 cmK1 could arise
from n2 mode (Table 6). The additional shoulder observed at
400 cmK1 according to Dawson et al. [15] might be
assigned as n4 mode, being drastically shifted due to
SiO4–SiO4 coupling.
Turning to the external vibrations of SiO4 groups, the
band at 388 cmK1 is assigned as translatory vibration
(Table 6) [15]. It involves principally displacements of the
lighter Si atoms, associated with the OSiO angle defor-
mations necessary to avoid change in Si–O bond lengths
[31]. The peaks from Zr–O translatory modes are expected
at lower frequencies (far-IR spectrum) around 200 cmK1
[15]. The agreement of the band frequencies and their
intensities observed in our spectrum with the corresponding
literature data is taken as a first indication that the studied
mineral is zircon.
The second step in the identification of zircon mineral is
interpretation of its Raman spectra (recorded with 1064 and
514 nm excitation lines) presented in Fig. 4a and b. As seen
from Fig. 4, in spite of the higher background and the worse
baseline of the spectrum recorded with higher wavelength
 P. Makreski et al. / Journal of Molecular Structure 744–747 (2005) 79–92 85

Table 5
Frequencies of the bands in the powder Raman spectrum of spessartine compared with the corresponding literature data

This worka,b Moore et al.c,d [12] Kolesov and Geigerc [24] Hofmeister and Chopelasc [14] Griffith [23] Assignmente
– – 162 162 Fe translations
183 w – 175 173 Fe translations
– – 196 194 SiO4 translations
228 w – 221 220 Fe translations
– – 269 229 – SiO4 translations
293 w – 302 300 – SiO4 translations
– – 321 318 – SiO4 translations
– – – 347 – SiO4 translations
354 m – 350 350 360 SiO4 rotations
377 sh – 372 372 – SiO4 rotations
413 vw – – 410 456 n2
454 vw – 475 472 470 n2
496 m 503 500 499 – n4
– – 522 521 – n2
557 m – 552 550 560 n2
607 vw – – 592 – n4
632 vw 617 630 628 – n4
838 w – 849 849 – n3
– – 879 878 880 n3
– – – 892 – n1
901 s 896 905 905 – n1
– – – 913 916 n3
976 v – – – – n3
1025 sh – 1029 1027 – n3
a
Excitation with 1064 nm.
b
Additional very weak bands appear at 684, 712 and 754 cmK1.
c
Single crystal.
d
The specimen contains 22% almandine, Fe3Al2(SiO4)3.
e
According to Hofmeister and Chopelas [14].

excitation line, in general, both spectra are identical. The

observed band frequencies are compared with the literature
analogues and presented in Table 7. The most characteristic
feature is the appearance of a strong band in the highest
frequency region of both spectra at 1008 cmK1 as well as
one weak at 973 cmK1 being assigned as a symmetric (n1)
and antisymmetric (n3) stretchings of the SiO4 units,
respectively. According to Griffith [23], the relatively high
frequency of the former band is mostly caused by the
structural factors rather then the very electronegative Zr
cation.
Four lower frequency Raman bands at 520, 438, 394 and
356 cmK1, which are also observed by other authors [23,26]
in the Raman spectrum of zircon at similar frequencies
(Table 7), are prescribed to the SiO4 bendings. The first and
the third one are very weak, whereas the strong intensity is
common for the second and the fourth band. Therefore, both
intense bands are attributed to the in-plane (n4) SiO4 modes,
whereas the remaining two arises from the out-of-plane
SiO4 bendings (n2).
If both Raman spectra for the same sample of zircon are
taken into account (Fig. 4a and b), the frequencies of
the resulting four bands registered in the region below
250 cmK1 are in very good agreement with the correspond-
ing single crystal Raman spectra [26] (Table 7), but Fig. 3. Infrared spectra of zircon (a) and titanite (b).
86 P. Makreski et al. / Journal of Molecular Structure 744–747 (2005) 79–92

Table 6
Frequencies and intensities of the bands in the powder infrared spectrum of zircon compared with the corresponding literature data

This work Dawson et al.a,b [15] Hubin and Tarte [16] Nicodomc [13] Rossmanc,d [17] Assignmente
388 m 389 390 390 m ‘Si vs Zr’ translations
400 sh 393 400 400 sh n4
434 m 430 436 440 w 438 m n4
450 sh – – – 455 w n2
611 s 608 615 612 s 610 s n4
898 s 885 905 895 s 895 s n3
979 w 989 1000 980 sh 980 w n3
1014 sh 1008 – 1010 sh 1015 sh n3
a
Single crystal.
b
Transverse modes are given.
c
Wavenumbers and intensities are approximate because are not given explicitly.
d
Additional medium band is observed around 320 cmK1.
e
According to Dawson et al. [15] except the shoulder at 450 cmK1.

surprisingly are not observed in the powder spectrum of this 608 cmK1, which according to Griffith does not originate
mineral [31]. On the other hand, the Raman bands at 200 from the silicate tetrahedra [23], probably arises from the
and 213 cmK1 (also registered in the IR spectrum of zircon Ti–O stretching vibration of the TiO6 octahedra. The
at 201 and 214 cmK1) [15] are assigned as translatory remaining bands in the Raman spectrum of titanite below
modes involving displacements of a rigid SiO4 group 400 cmK1 (except the absent band at 310 cmK1) are also in
relative to the Zr cations. agreement with the data published by Salje et al. [27],
contributing to the successful identification of titanite
4.1.3. Titanite, CaTiOSiO4 mineral specimen.
The infrared spectrum of the studied titanite sample
(Fig. 3b) is practically identical with the corresponding
published, but not discussed spectrum of this mineral [13]
(Table 8). As seen from the spectrum, the n3 mode of the
SiO4 groups is split into three components with frequencies
at 953, 897 and 873 cmK1, being very close to the literature
data. Triple splitting is also observed for the n4 mode (566,
472 and 432 cmK1), compared to the two components of the
n4 mode mentioned in the literature (Table 8). It seems that
the missing weak peak is overlapped by the strong band at
around 430 cmK1 in the titanite spectrum of Nicodom [13].
The very weak band at 377 cmK1 as well as a shoulder at
407 cmK1 are also observed in the studied spectrum and
assigned as the n2 modes (Table 8). The broad band at
700 cmK1 followed by additional two shoulders in the
800–600 cmK1 region (Fig. 3 and Table 8) is probably due
to the vibrations of the present TiO6 octahedra (Table 1) in
the structure of titanite (see forthcoming discussion of the
Raman spectrum).
As seen from the practically identical Raman spectra of
titanite recorded with 1064 and 514 nm excited lines (Fig. 4,
c and d), six fundamental bands due to the silicate modes are
observed in the high frequency 1000–400 cmK1 region
(Table 9). Three among them, assigned as bending n4
modes, have the same frequencies with those registered by
Griffith [23] (548, 467 and 425 cmK1). The same is also the
frequency of the maximum at 856 cmK1 prescribed to
the symmetric SiO4 stretching vibrations of n1 type. On the
other hand, subtle frequency difference between our and
the literature data is observed for the both highest frequency
bands registered at 912/911 and 872/873 cmK1 which Fig. 4. Micro-Raman spectra of zircon (a, b) and titanite (c, d) excited with
are attributed to the n3 modes. The very strong band at 1064 and 514 nm lines, respectively.
 P. Makreski et al. / Journal of Molecular Structure 744–747 (2005) 79–92 87

Table 7 Table 9
Frequencies and intensity of the bands in the powder Raman spectrum of Frequencies and intensities of the bands in the powder Raman spectrum of
zircon compared with the corresponding literature data titanite compared with the corresponding literature data

This worka,b This workc Griffith [23] Calligaro Assign- This worka This workb Griffith [23] Salje et al.c Assigne-
et al.d [26] mente [27] mentd
180 vw 180 75 m
200 vw 200 vw 195 ZrCSiO4 110 m
translations 146 vw 140 s
– 213 vw – 215 ZrCSiO4 164 w 170 s
translations 208 sh –
224 m 224 m – 225 233 vw 233 vw 230 vw
356 vs 356 s 356 vs 350 n2 253 m 253 m 250 vs
394 vw 394 w 392 w n2 286 sh 286 sh 280 w
438 s 438 s 439 s 440 n4 310 m
– 520 w 460 w 530 n4 316 w 317 w 325 w
769 m 775 vw – 917 333 vw 334 vw 340 m
973 w 973 m 975 w 979 n3 425 w 424 w 425 415 w n4
1008 vs 1008 vs 1010 vs 1014 n1 467 s 468 s 467 455 s n4
a
548 m 549 m 548 530 s n4
Excitation with 1064 nm. 608 vs 607 vs 608 595 vs
b
Additional very weak bands appear at 1056, 1090, 1112, 1466 and 856 m 856 m 856 860 vw n1
1515 cmK1. 872 m 873 m 874 880 w n3
c
Excitation with 514 nm. 912 w 911 w 920 915 vw n3
d
Single crystal.
e a
According to Griffith for the bands above 350 cmK1 [23]. Excitation with 1064 nm (Fig. 4c).
b
Excitation with 514 nm (Fig. 4d).
4.1.4. Olivine, (Mg,Fe)2SiO4 c
Wavenumbers and intensities are approximate because are not given
Generically, the term olivine (Mg,Fe)2SiO4 is used for explicitly.
d
mixture consisted of various content of isomorphous According to Griffith [23].
forsterite, Mg2SiO4 and fayalite, Fe2SiO4, being the end-
expressed for the bands above 600 cmK1 (Table 10) that
members of this series.
enables to discriminate the various olivine species. The
The infrared spectra of both mineral forms are discussed
application of this criterion to the infrared spectrum of our
by various authors [11,13,18,19] and are rather similar. In
olivine specimen shows that the band frequencies are closer
order to compare them with our infrared spectrum (Fig. 5a)
the obtained data are summarized in Table 10. According to to the corresponding bands in the spectrum of forsterite,
Burns and Huggins [19], all infrared bands of the forsterite– Mg2SiO4, analogue. Namely, all expected bands in this
fayalite series show a frequency shift of peak maxima to region of the forsterite spectrum are observed in our
lower values with iron content increasing. It means that
variation of the anion frequencies with the nature of
the cation in the olivines gives opportunity to determine
the olivine composition from the IR spectra. It is mostly
Table 8
Frequencies and intensities of the bands in the powder infrared spectrum of
titanite compared with the corresponding literature data

This work Nicodoma [13] Assignment

377 vw n2
407 sh 407 sh n2
432 s 438 s n4
472 w – n4
500 sh –
566 s 564 m n4
578 sh 582 sh
586 sh –
623 sh 617 vw
700 m 710 vw
744 sh 748 w
873 s 868 s n3
897 s 897 s n3
953 sh 957 s n3
a
Wavenumbers and intensities are approximate because are not given Fig. 5. Infrared (a) and micro-Raman (b) spectrum of olivine (var.
explicitly. forsterite).
88 P. Makreski et al. / Journal of Molecular Structure 744–747 (2005) 79–92

Table 10
Frequencies and intensities of the bands in the powder infrared spectrum of olivine compared with the corresponding literature data

This work Nicodoma [13] Tarte [18] Burns and Huggins [19] Moenke [11] Assignmentb
Mg2SiO4 Fe2SiO4 Mg2SiO4 Fe2SiO4
379 vw 380 vw – 378 vw – –
401 sh 399 s 402 sh – 399 vw – –
417 vs – 422 s 420 sh 415 vs – 418 s n2
470 w 470 m 465 m 481 s 469 w 472 s 475 w
505 vs 504 s 510 vs 509 m 506 vs 506 m 516 s n4
522 sh 523 sh – – – – –
547 sh 550 sh – – – – –
577 vw – – 566 s – 558 vs –
608 s 607 s 615 s – 605 s – – n4
839 w 838 w 842 w 832 m 838 w 827 w 848 m n1
886 vs 888 vs 892 vs 879 vs 885 vs 872 vs – n3
915 sh 914 sh – 920 w – 914 w 898 s
955 w 956 vw 964 w 945 sh 954w 945 s 950 w
982 vs 982 s 990 s 963 sh 982 vs – – n3
1000 sh 1001 sh 1001 sh – – – 1002 m n3
a
Wavenumbers and intensities are approximate because explicite numerical data are not given.
b
According to Tarte [18].

spectrum of olivine, although the shoulders at 1000 and literature data for the peaks below 700 cmK1 where the
915 cmK1 are not registered by Burns and Huggins [19], bending modes are expected is also observed (Table 11).
whereas only the shoulder at 1001 cmK1 is observed in the
infrared spectrum of forsterite studied by Tarte [18].
4.1.5. Kyanite, Al2OSiO4
According to the latter author, the strong bands in our
At least two clearly isolated band regions are observed in
spectrum at 886 and 982 cmK1 as well as the shoulder at the spectrum of the mineral contemplated as kyanite
1000 cmK1 could be assigned as n3 stretching SiO4 (Fig. 6a). Starting from the highest frequency 1100–
vibration, whereas the weak one at 839 cmK1 is prescribed 800 cmK1 region, four bands due to the stretching SiO4
to the symmetric stretching SiO4 mode. As a further vibrations are registered (Table 12, Fig. 6a). Contrary to all
evidence for the correct identification of the forsterite other studied nesosilicates, the IR spectrum of kyanite
analogue of the studied olivine specimen (instead of fayalite shows an extremely large number of bands in the region
or some appropriate mixtures) are the bands originating below 800 cmK1, where 17 maxima appear. The 5 highest
below 450 cmK1 which are absent in the later cases [19] frequency bands from 620 to 730 cmK1 according to Farmer
(Table 10). The remaining strong peaks at 608 and
505 cmK1 are prescribed to the n4 mode, whereas the Table 11
Frequencies and intensities of the bands in the powder Raman spectrum of
intense maximum at 417 cmK1 is attributed to the n2 mode. olivine (forsterite) compared with the corresponding literature data
Contrary to the series of the hydrous olivine mineral
This worka Griffith [23] Guyot et al.b Assignmentc
types where the characteristic OH absorption bands have
[28]
been observed [32,33], no bands are registered in the OH Mg2SiO4 Fe2SiO4
stretching region of our olivine specimen, suggesting that it 207 w – –
is nominally anhydridous. 255 w – –
329 w 327 – n2
The successful identification of the studied mineral as
394 vw 380 380 n2
forsterite by infrared spectroscopy is, at some extent, 431 w – –
supported by the view of its low quality Raman spectrum 463 vw 465 – n4
(Fig. 5b). Namely, the strongest peaks observed in the 546 w 546 550 n4
601 w 602 608 n4
Raman spectrum at 823 and 855 cmK1 correspond to the
648 w – –
most intense bands registered in the literature at almost 696 w – –
the same frequencies [23,28] (Table 11), arising from the 766 w – –
n1 and n3 stretching vibrations of the SiO4 tetrahedra, 823 vs 823 828 824 n1
respectively. Additional two bands in our spectrum (at 855 vs 860 – 855 n3
920 w – – 920
920 and 954 cmK1), followed by analogue ones at very 954 w 950 – 960 n3
close frequencies in the spectra published by Griffith [23] a
Excitation with 1064 nm.
and Guyot et al. [28] (Table 11), are prescribed to the b
Only stretching SiO4 modes are discussed.
SiO4 stretchings. Some similarities between our and c
According to Griffith [23].
 P. Makreski et al. / Journal of Molecular Structure 744–747 (2005) 79–92
Fig. 6. Infrared spectra of kyanite (a) and staurolite (b, c). The band intensities between spectrum b and c are not directly comparable.
[31] could be assigned as SiO4 deformation vibrations. The
band frequency increase and the strong absorption in
kyanite are explained with the following structural factors:
(i) the smaller Si–O–Al bond angles in kyanite (124.58) [21]
which influence more expressed Al–O stretching character
of the O–Si–O bendings, and (ii) short Al–O distances
(1.81–1.86 Å) [21]. Anyhow, the comparison of the IR band
frequencies of kyanite with the corresponding published,
but not discussed data [13], undoubtedly confirms the
identification of this mineral as kyanite and again
demonstrates that the IR technique is very powerful tool
in identification of this mineral group.
Extremely large number of bands also appears in the
Raman spectrum of kyanite (Fig. 7a and Table 12).
Similarly to the above discussion regarding the IR spectrum,
five highest frequency bands in the 1015–900 cmK1 region
are prescribed to the split bands arising from the SiO4
stretching modes n3 and n1. The remaining three lower
frequency bands in the 670–620 cmK1 region are attributed
to the bands due to the SiO4 bending n4 modes which also
split into three components.
From the above discussion of the IR and Raman spectra
of kyanite it is evidently that the vibrations of the SiO4
groups are dominant which implies that a weak interaction
between the AlO6 octahedra and the silicate tetrahedra exist
(Table 1) [29].
4.1.6. Staurolite, Fe2Al9O6(SiO4)4(OH)2
The powder IR spectrum of staurolite (Fig. 6b) shows, to
some extent, similarities with the corresponding spectrum of
89
kyanite being influenced by their common structural
features (Section 3 and Table 1). Consequently, its spectrum
is characterized by appearance of two well-separated
regions. The higher frequency region amounting from
1100 to 800 cmK1 is represented by a very strong and
complex band with the maximum at 971 cm K1
accompanied by additional four weak to medium peaks or
shoulders on its higher and lower frequency side (Table 13).
It is unambiguous that all these bands arise from the
stretching vibrations of the SiO4 units, mostly of them
(including the mentioned one) belonging to the antisym-
metric stretchings. The strong similarity of our spectrum of
staurolite with the corresponding literature data is observed
not only for this region, but also for the bands between 700
and 590 cmK1. These maxima, mainly assigned as SiO4
bendings, appear almost at the same frequencies with
the literature data [13], where the greatest band shifting does
not exceed 5 cmK1.
The vibrations of the present OH groups in the structure
of staurolite (only this studied mineral contains OH groups)
are manifested by the bands above 3400 cmK1 (Fig. 6c),
where three pairs of bands are distinguished: the first
characterized with the peaks at 3426, 3451 cmK1, the
second at 3520 and 3571 cmK1 and the third one at 3622
and 3675 cmK1. As seen from the Table 13, rather
expressed agreement between our spectrum and polarized
staurolite spectra from Koch-Müller et al. exists [22].
According to this group of authors, both highest frequency
bands in the region III could not be interpreted on the basis
of the proton positions known for staurolite, assigning them
90 P. Makreski et al. / Journal of Molecular Structure 744–747 (2005) 79–92

Table 12
Frequencies and intensity of the bands in the powder IR and Raman spectrum of kyanite compared with the corresponding literature data

Infrared Raman
a b
This work Nicodom [13] Assignment This work Mernagh and Liu [29] Assignmenta
384 w
395 vw 302
400 vw 290 w
438 m 436 w 303 vw 325
– 440 w 314 m
467 m 466 m 338 m
491 sh 490 sh 354 vw 360
505 m 503 m 373 m 386
529 sh – 398 m
546 w 543 w 405 m 405
567 vw 564 vw 417 s 419
589 vw 588 sh 432 w 437
605 w 603 vw 451 s
623 w 623 vw nbending (SiO4) 460 vw
638 w 638 vw nbending (SiO4) 477 vw 486
675 m 675 w nbending (SiO4) 499 vs
713 w 710 sh nbending (SiO4) 524 w
732 vw 732 vw nbending (SiO4) 575 m 562
898 w 897 w nstretching (SiO4) 618 w nbending (SiO4)
941 m 940 s nstretching (SiO4) 650 w nbending (SiO4)
997 m 1002 m nstretching (SiO4) 668 w 669 nbending (SiO4)
1035 s 1037 m nstretching (SiO4) 902 m nstretching (SiO4)
911 m nstretching (SiO4)
964 s 952 nstretching (SiO4)
970 s nstretching (SiO4)
1013 m nstretching (SiO4)
a
Wavenumbers and intensities are approximate because are not given explicitly.
b
Vibrational modes from the SiO4 tetrahedra according to Farmer [31].
c
According to Griffith [23].

to an additional proton (H3) different from the both previous and kyanite, the bands at 715 and 767 cmK1 could also be
known in the structure of this mineral, H1 and H2. It is not assigned as the SiO4 bending vibrations.
excluded that our staurolite mineral sample also contains
three structurally different hydrogen atoms. Further struc-
tural studies should, however, be carried out in order to
5. Conclusions
confirm the above presumption. In spite of that, the
identification of the studied mineral as staurolite is undoubt.
It was shown that the identification of the almandine,
Contrary to the expressed similarity between the infrared
spessartine, zircon, titanite and kyanite nesosilicate
spectra of kyanite and staurolite (Fig. 6), their Raman
spectra are rather different (Fig. 7). The lower quality
Raman spectrum of staurolite contains smaller number of
less resolved bands. To the best of our knowledge, there are
no literature data regarding the Raman spectrum of this
mineral. The lack of the corresponding literature data makes
more difficult to use our low quality Raman spectrum for the
identification purposes. In spite of that, probably the hardly
observed three very weak bands above 900 cmK1 could be
assigned as the stretching SiO4 vibrations (Table 14).
Taking into account the structural similarities with kyanite
(Table 1) and the assignation of the Raman bands in its
spectrum in the region between 670 and 620 cmK1, the
medium band at 650 cmK1 in staurolite spectrum is
prescribed to the silicate bendings (Table 14). According
to the above assignation of the infrared spectra of staurolite Fig. 7. Micro-Raman spectra of kyanite (a) and staurolite (b) excited with
514 nm line.
 P. Makreski et al. / Journal of Molecular Structure 744–747 (2005) 79–92 91

Table 13 one should be aware that some structural changes in the

Frequencies and intensities of the bands in the powder infrared spectrum of mineral could happen during the Raman experiment
staurolite compared with the corresponding literature data
performing by the use of different excitation lines, as it
This work Nicodoma Koch-Müller et al. [22] Assign- was the case with the studied almandine sample.
[13] mentb In general, it could be concluded that in the case of
(010) Ekc (010) Eka nesosilicates, the IR spectroscopy is the more powerful
399 vw 407 vw technique for mineral identification compared to the Raman
432 m 433 w experiment. In the latter case, the bands originating from
487 m 484 w
SiO4 modes are weak due to the small degree of p-bonding
525 sh 522 vw
543 w 540 vw in the Si–O linkages [23].
593 m 590 w nbending
(SiO4)
640 sh 645 vw nbending
(SiO4) Acknowledgements
684 vw 689 sh nbending
(SiO4)
847 sh 843 w nstretching The financial support from the Ministry of Education and
(SiO4) Science of the Republic of Macedonia is gratefully
898 sh 897 w nstretching acknowledged. The authors cordially thank Dr. Minjaš
(SiO4) Žugik from Solid State Physics Group, King’s College,
938 sh – nstretching
(SiO4)
London, UK, as well as Professor. Branko Kaitner and
970 s 963 s nstretching Tomislav Biljan, from the Faculty of Science, University of
(SiO4) Zagreb, Zagreb, Croatia, for obtaining the Raman spectra.
1022 m 1022 w nstretching
(SiO4)
– – 3340 3358 nH1
3426 s 3420 m 3424 3420 nH1
3451 sh – 3450 3442 nH1 References
– – 3468 3465 nH1
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3675 m – 3677 3677 nH3 25–32.
[3] V. Stefov, G. Jovanovski, B. Soptrajanov, B. Minceva-Sukarova,
a
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