11th International GeoRaman Conference (2014)

5061.pdf

AB INITIO CALCULATED AND EXPERIMENTALLY MEASURED RAMAN SPECTRA OF

SPODUMENE (LiAlSi2O6). C. Stangarone1, M. Prencipe2, L. Mantovani1, D. Bersani1, M. Tribaudino1,
P.P. Lottici1, 1Universit di Parma, Dipartimento di Fisica e Scienze della Terra, Parco Area delle Scienze 7/A,
43124 Parma, Italy, claudia.stangarone@studenti.unipr.it, 2Universit di Torino, Dipartimento di Scienze Mineralogiche e Petrologiche, via Valperga Caluso 35, 10125 Torino, Italy.

Introduction: Spodumene is a Li and Al monoclinic chain silicate having C2/c space group at ambient condition. The importance of this pyroxene is due
to the presence of lithium, which makes it one of the
principal sources of this metal, used in glass and ceramic industries. The aim of this study is to improve
the interpretation of Raman experimental spectra of
spodumene, by exploiting the accuracy of the quantum
mechanical calculations.
An ab initio HF/DFT study of Raman spectra of
Spodumene has been performed with the program
CRYSTAL14 [1] which employes localized, gaussiantype basis sets. The chosen Hamiltonian was WC1LYP
which is based on the Wu-Cohen exchange functional,
corrected by a fraction (16%) of non-local exact Hartree-Fock exchange, and Lee-Young-Parr correlation
functional [2] [3].
The simulated data have been compared with experimental Raman spectroscopy measurements on a
natural sample of spodumene, that was already studied
by single crystal X-Ray diffraction [4]. The calculation
provided an excellent agreements with the experimental data. In particular, all the 30 expected Raman
active vibrational modes (14 Ag and 16 Bg) have been
recognized on the experimental polarized spectra,
showing average absolute difference of 4.8 cm-1 with
the frequencies calculated. Intensities are also in good
agreement with the experimental data.
Raman spectra have been taken on the (100) and
(010) surfaces of the sample. The spectra were recorded with 632.8 nm excitation ligth from a HeNe laser
in a backscattering geometry using a Horiba-JobinYvon LabRAM microspectrometer (300 mm focal
length) equipped with an Olympus BX40 microscope.
The spectral resolution was about 2 cm-1. The Rayleigh
radiation was blocked by a reflective volume Bragg
grating notch filters BragGrate (OptiGrate), and the
backscattered Raman light was dispersed by a 1800
grooves/mm holographic grating on to a Peltier cooled
CCD, consisting of an array of 1024 256 pixels. The
entrance slit width was fixed at 150 m.
The laser power was set less than 5 mW on the
sample, by means of a series of density filters, to avoid
uncontrolled thermal effects. Spectra were collected
both by using a 4x objective (NA=0.1) for preliminary
scanning and ultra-long working distance 50x microscope objective (NA=0.55) with spatial resolution of
about 1.0 m on the sample. Typical exposures were
for 10120 s, repeated 35 times. The system was fre-

quently calibrated using the 520.6 cm-1 Raman band of

silicon and by suitable crystalline standards.

Figure 1 - Raman spectrum taken in parallel polarization on the (010) face of spodumene and the corresponding calculated intensity pattern, according to
Crystal14.
The crystal has been mounted on a routable goniometer stage and oriented under the microscope. The
Raman spectra were taken in different geometries in
order to select the Ag and the Bg symmetry modes. Fig.
1 reports a typical Raman spectrum taken on the (010)
surface, where only the Ag modes should be observed.
All the 14 Ag modes have been identified and their frequencies ar reported in Table1.
To select the Bg symmetry modes, crosspolarization measurements were made on the (100) and
(001) surfaces. On the (100) surface both Ag and Bg
modes are observed, whereas the backscattering along
a (001) surface gives Bg modes (some leakage of the
most intense Ag modes is present).
Figure 2 reports the cross-polarization spectra. All
the expected 16 Bg modes (indicated by asterisks) are

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

11th International GeoRaman Conference (2014)

easily discernible and their frequencies are reported in

Table 1.

5061.pdf

Table 1 - Experimental and calculated frequencies.

RRUFF Ref. [5] Calculated
147

130.3

146

(Bg )

155

132.8

130

(Ag )

185

181.1

186

(Ag )

227

219.2

226.5

(Bg )

249

235.6

246

(Bg )

251.1

250

(Ag )

261

260

(Bg )

288.7

293

(Ag )

295

297.8

297

(Bg )

326

328.2

323

(Bg )

330

329

(Ag )

349.4

354

(Ag )

13

362.3

359

(Bg )

14

381

387

(Bg )

247

292

10
11

347

12

353

354

15

390

392

391.4

392

(Ag )

16

416

416

419.1

416

(Bg )

17

440

441

443.6

441

(Ag )

18

520

522

522.7

521

(Ag )

538.5

533

(Bg )

19
20

545

547.1

543

(Bg )

21

583

591.5

585

(Ag )

628.1

615

(Bg )

710.1

705

(Ag )

22

In Table 1 we report the measured frequencies of

the 14Ag + 16Bg Raman active modes, compared with
the
results
reported
in
http://rruff.info/spodumene/display=default/R050252
and in Ref. [5]. The average absolute difference between measured and calculated frequencies is about
4.8 cm-1.

Symmetry

Figure 1 - Raman spectra taken in cross- polarization

on the (100) and (001) surfaces of spodumene (the asterisks indicate the 16 Bg symmetry modes) and the
corresponding calculated intensity pattern. Residual
Ag symmetry modes are also present.

Experimental

23

704

24

784

793.2

784

(Bg )

25

809

880.3

883

(Bg )

26

975

972

977

(Ag )

27

1017

1026.8

1020

(Ag )

1053.4

1052

(Bg )

28

708

29

1071

1074.2

1072

(Ag )

30

1101

1110

1103

(Bg )

References: [1] Dovesi R.. (2014) CRYSTAL14 User's

Manual (University of Torino), [2] Wu Z. and Cohen R. E.
(2006) Phys. Rev. B 73, 235116, [3] Lee C. et al. (1988)
Phys. Rev. B 37, 785-789, [4] Tribaudino M. et al. (2003)
Canadian Mineral. 41, 521-527, [5] Pommier C. J. S. et al.
(2003) J. Raman Spectrosc. 34, 769775.

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