The Raman spectrum of grossular garnet: a quantum mechanical simulation of wavenumbers and intensities

Raman spectroscopy is a standard and powerful investigation technique for minerals, and garnet is one of the most observed and visible minerals, undoubtfully important both as a witness of our planet’s evolution and as a main component in many high-tech applications. This paper presents the Raman sp...

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Main Authors: Maschio, L., Demichelis, Raffaella, Orlando, R., De La Pierre, M., Mahmoud, A., Dovesi, R.
Format: Journal Article
Published: John Wiley & Sons Ltd 2014
Subjects:
Online Access:http://hdl.handle.net/20.500.11937/32171
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author Maschio, L.
Demichelis, Raffaella
Orlando, R.
De La Pierre, M.
Mahmoud, A.
Dovesi, R.
author_facet Maschio, L.
Demichelis, Raffaella
Orlando, R.
De La Pierre, M.
Mahmoud, A.
Dovesi, R.
author_sort Maschio, L.
building Curtin Institutional Repository
collection Online Access
description Raman spectroscopy is a standard and powerful investigation technique for minerals, and garnet is one of the most observed and visible minerals, undoubtfully important both as a witness of our planet’s evolution and as a main component in many high-tech applications. This paper presents the Raman spectrum of grossular, the calcium–aluminium end-member of garnets (Ca3Al2Si3O12), as computed by using an ab initio quantum-mechanical approach, an all-electron Gaussian-type basis set and the hybrid B3LYP functional. The wavenumbers of the 25 Raman active modes are in excellent agreement with the available experimental measurements, with the mean absolute difference being between 5 and 8 cm1. The apparent disagreement between a few experimental vs calculated data can be easily justified through the analysis of the corresponding calculated peak intensities, which is very low in all of these cases. The intensities of the Raman active modes of grossular were calculated here for the first time, thanks to a recent implementation by some of the present authors that allow for accurate predictions of the Raman spectra of minerals. To the authors’ knowledge, there are no tabulated data sets for Raman intensities of grossular, although qualitative information can be extracted from the published spectra. This study can then be considered as an accurate reference data set for grossular, other than a clear evidence that quantum-mechanical simulation is an actual tool to predict spectroscopic properties of minerals.
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spelling curtin-20.500.11937-321712017-09-13T15:18:08Z The Raman spectrum of grossular garnet: a quantum mechanical simulation of wavenumbers and intensities Maschio, L. Demichelis, Raffaella Orlando, R. De La Pierre, M. Mahmoud, A. Dovesi, R. grossular Raman intensities ab initio calculation wavenumbers CRYSTAL code Raman spectroscopy is a standard and powerful investigation technique for minerals, and garnet is one of the most observed and visible minerals, undoubtfully important both as a witness of our planet’s evolution and as a main component in many high-tech applications. This paper presents the Raman spectrum of grossular, the calcium–aluminium end-member of garnets (Ca3Al2Si3O12), as computed by using an ab initio quantum-mechanical approach, an all-electron Gaussian-type basis set and the hybrid B3LYP functional. The wavenumbers of the 25 Raman active modes are in excellent agreement with the available experimental measurements, with the mean absolute difference being between 5 and 8 cm1. The apparent disagreement between a few experimental vs calculated data can be easily justified through the analysis of the corresponding calculated peak intensities, which is very low in all of these cases. The intensities of the Raman active modes of grossular were calculated here for the first time, thanks to a recent implementation by some of the present authors that allow for accurate predictions of the Raman spectra of minerals. To the authors’ knowledge, there are no tabulated data sets for Raman intensities of grossular, although qualitative information can be extracted from the published spectra. This study can then be considered as an accurate reference data set for grossular, other than a clear evidence that quantum-mechanical simulation is an actual tool to predict spectroscopic properties of minerals. 2014 Journal Article http://hdl.handle.net/20.500.11937/32171 10.1002/jrs.4527 John Wiley & Sons Ltd fulltext
spellingShingle grossular
Raman intensities
ab initio calculation
wavenumbers
CRYSTAL code
Maschio, L.
Demichelis, Raffaella
Orlando, R.
De La Pierre, M.
Mahmoud, A.
Dovesi, R.
The Raman spectrum of grossular garnet: a quantum mechanical simulation of wavenumbers and intensities
title The Raman spectrum of grossular garnet: a quantum mechanical simulation of wavenumbers and intensities
title_full The Raman spectrum of grossular garnet: a quantum mechanical simulation of wavenumbers and intensities
title_fullStr The Raman spectrum of grossular garnet: a quantum mechanical simulation of wavenumbers and intensities
title_full_unstemmed The Raman spectrum of grossular garnet: a quantum mechanical simulation of wavenumbers and intensities
title_short The Raman spectrum of grossular garnet: a quantum mechanical simulation of wavenumbers and intensities
title_sort raman spectrum of grossular garnet: a quantum mechanical simulation of wavenumbers and intensities
topic grossular
Raman intensities
ab initio calculation
wavenumbers
CRYSTAL code
url http://hdl.handle.net/20.500.11937/32171