THE RAMAN SPECTRUM OF TRICLINIC ALBITE: A COMPARISON BETWEEN AB INITIO

CALCULATED AND MEASURED FREQUENCIES. I. Aliatis1, E. Lambruschi1, L. Mantovani1, D. Bersani1, S.

And3, G. D. Gatta2, P. Gentile3, E. Salvioli-Mariani1, M. Prencipe4, M. Tribaudino1, P.P. Lottici1, 1Universit di
Parma, Dipartimento di Fisica e Scienze della Terra, Parco Area delle Scienze 7/A, 43124 Parma,
Italy,irene.aliatis@difest.unipr.it, 2Universit di Milano, Dipartimento di Scienze della Terra, via Botticelli 23, 20133
Milano, Italy, 3Universit di Milano Bicocca, Dipartimento di Scienze dell'Ambiente e del Territorio e di Scienze
della Terra, piazza della Scienza 4, 20126 Milano, Italy, 4Universit di Torino, Dipartimento di Scienze della Terra,
via Valperga Caluso 35, 10125 Torino, Italy.
Introduction: Albite, NaAlSi3O8, is the sodic endmember of plagioclase and alkali feldspar-group
minerals. Among framework silicates, albite is one of
the common rock-forming minerals of Earths crust. It
occurs in granite pegmatite, metamorphic and
sedimentary rocks. The basic building unit of albite
framework consists of rings of four tetrahedra (four
symmetrically non-equivalent sites in triclinic
structure, labeled T1o, T1m, T2o and T2m, and only
two in monoclinic one, i.e.T1 and T2) forming
crankshaft-like chains. The 3D structure forms
tetrahedral cages with Na ions in the cavities [1,2]. Al
atoms occupy the T1o tetrahedral site of the fourmembered tetrahedral rings in the ordered structure,
known as low albite (triclinic). Disordered albite
undergoes a triclinic-to-monoclinic phase transition
near 980 C, into monoalbite, where the Al and Si are
statistically distributed between the tetrahedral sites
and the complete ordering is lost. Albite exhibits also
two high temperature triclinic phases: analbite,
essentially completely disordered under 980 C, which
inverts to monoalbite on heating, and high albite,
resulting from diffusive transformation in the (Si-Al)
distribution [1].
Low albite is generally described by a non-standard
. The factor group analysis at
space group C 1
point predicts 39 Ag Raman active modes and 39 Au
infrared active modes (including the 3 acoustic
modes).
McKeown [3] reported the unpolarized Raman
spectrum of a triclinic crystal of albite at room
temperature and studied the evolution of the Raman
features from 25 C to above the 1118 C melting
temperature (through the triclinic-to-monoclinic
displacive transition). The vibrational assignments in
ref. [3] were made on LD calculations, based on
valence force potentials, where the parameters were
chosen in order to obtain the best fit with fundamental
vibrational frequencies derived from the experimental
spectrum.
Accurate Raman calculations on triclinic minerals are
not so frequent in scientific literature. The aim of this
study is the comparison between the experimentally
measured Raman spectrum of a natural triclinic sample
and the ab initio calculated Raman spectrum of low
albite.

By using the CRYSTAL14 program [4],

calculations were made at the hybrid HartreeFock/Density Functional level (HF/DFT): the
WC1LYP Hamiltonian, which provides excellent
agreement between calculated and experimentally
measured vibrational frequencies (see e.g. [5]), was
employed.

Fig. 1: Comparison between the ab initio calculated

Raman spectrum and two experimentally measured
unpolarized spectra collected on (010) face, at = 0
and = 90 from the a crystallographic axis.
Results: Measurements have been performed on
an albite sample, var. cleavelandite, from Minas
Gerais, Brasil. Phase identification of the sample was
checked by powder X-ray diffraction; chemical

Abstract for 11th GeoRaman International Conference, June 15-19, 2014, St. Louis, Missourri, USA

analyses indicated close to end-member composition,

with K2O and CaO impurity concentrations of 0.32 and
0.19 wt%, respectively. The unit-cell constants were
measured by single-crystal X-ray diffraction, with: a =
8.1395(5) , b = 12.7838(7) , c = 7.1597(6) , =
94.242(6), = 116.590(7), = 87.674(5), V =
664.35(9) 3. The estimated order parameter Q od is 1,
complete order. Qod defines the state of Al/Si order
relative to completely ordered albite and it was
calculated from the averaged <TO> bond lengths
determined by single-crystal structure refinements
according to the ref. [6].

Measured
frequencies
66.6
70.8
86.3
114.6
145.2
155.9
162.7
170.0
179.5
186.4
209.9
251.6
269.1
290.8
310.7
328.7
347.9
399.6
407.6
416.0
456.6
479.1
490.0
507.5
579.1
633.1
647.1
721.5
763.7
775.9
815.7
977.3
1008.4
1014.4
1032.5
1046.2
1099.4
1115.4
1152.0

LD
frequencies
[3]
67
89
111
140
150
160
168
176
183
207
216
250
268
289
307
327
346
367
396
406
455
477
505
528
578
632
645
720
720
762
814
977
1005
1030
1046
1098
1116
1151
1170

Ab initio
calculated
frequencies
66
73
92
118
148
151
161
168
176
187
207
254
271
290
310
329
350
398
410
419
466
485
492
513

Tab. 1: Comparison between the measured and

calculated frequencies (LD vs ab initio). All
frequencies are expressed in cm-1.
Raman spectra have been collected on the (010)
face of different albite fragments with a Horiba JobinYvon LabRAM apparatus ( = 632.8 nm). Samples
were mounted on a goniometric stage and oriented
under the 50X microscope: the incident beam
polarization was made to correspond to the a
crystallographic axis (=0). The Raman spectra for
=0 and =90 are reported in Fig.1, together with
the calculated spectra.
The comparison between the frequencies measured
by Raman spectroscopy on the natural sample with
those calculated by HF/DFT is reported in Table 1. All
the expected 39 Ag modes have been identified in the
Raman spectra and their frequencies well correspond
to the calculated ones (the average absolute
discrepancy (<||>) is ~ 3 cm-1; the maximum
discrepancy (||max) is ~ 10 cm -1). The very good
quality of the WC1LYP results allowed for reliable
assignments to specific patterns of atomic vibrational
motion (normal modes).
Acknowledgement: One of the authors (I.A.) is
indebted to Fondazione Cariparma, Parma, for
financial support.
References: [1] Ribbe P.H., Ed. (1983) Feldspar
Mineralogy, 2nd ed., Mineralogical Society of America,
Chantilly, VA. [2] Smith J.V. (1974) Feldspar Minerals
I. Crystal Structure and Physical Properties, SpringerVerlag, Heidelberg. [3] McKeown D. A. (2005) Am.
Mineral., 90, 1506-1517. [4] Dovesi R. et al.
University of Torino, Torino, 2014. [5] Prencipe M. et
al. (2012) Eur. J. Mineral., 24, 457-464. [6] Tribaudino
M. et al. (2010) Contrib. Mineral. Petrol., 160, 899908.

579
634
649
724
768
784
825
972
1001
1012
1037
1044
1102
1117
1156

Abstract for 11th GeoRaman International Conference, June 15-19, 2014, St. Louis, Missourri, USA