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 HoribaJobin-Yvon 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 frequently 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).

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

Figure 2 reports the cross-polarization spectra. All

the expected 16 Bg modes (indicated by asterisks) are
easily discernible and their frequencies are reported in
Table 1.
RRUFF Ref. [5] Calculated

Experimental

Symmet
ry

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
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 )

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

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.
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.
Table 1 - Experimental and calculated frequencies.
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