Ab initio investigation of majorite and pyrope garnets: Lattice dynamics and vibrational spectra

A detailed ab initio quantum-mechanical characterization is presented of the vibrational properties of pyrope and majorite garnets, using the hybrid B3LYP functional and large all electron Gaussian type basis sets. Discussed quantities include infrared (both TO and LO) and Raman frequencies, normal...

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Main Authors: De La Pierre, Marco, Belmonte, D.
Format: Journal Article
Published: Mineralogical Society of America 2016
Online Access:http://hdl.handle.net/20.500.11937/33346
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author De La Pierre, Marco
Belmonte, D.
author_facet De La Pierre, Marco
Belmonte, D.
author_sort De La Pierre, Marco
building Curtin Institutional Repository
collection Online Access
description A detailed ab initio quantum-mechanical characterization is presented of the vibrational properties of pyrope and majorite garnets, using the hybrid B3LYP functional and large all electron Gaussian type basis sets. Discussed quantities include infrared (both TO and LO) and Raman frequencies, normal mode coordinates, spectroscopic intensities, mode Grüneisen parameters, isotopic substitution, and infrared and Raman spectra. Comparison with data available in the literature demonstrates the accuracy of the adopted method. Main spectral features of the two garnets are interpreted in terms of either symmetry analysis or structural contributions to the vibrational modes. Missing peaks in the experiments are discussed in light of the simulated spectra. The present high-quality vibrational data can be used to compute thermal expansivities at high-pressure and high-temperature conditions. Calculated values for majorite at the bottom of the mantle transition zone (aV = 2.2 × 10-5 K-1 at T = 1500 K and P = 20 GPa) turn out to be sensibly greater (up to three times) than those currently adopted in geophysical thermodynamic databases, thus calling for a careful revision of the numerical models for thermo-chemical convection of the Earth’s mantle
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spelling curtin-20.500.11937-333462017-10-02T02:28:10Z Ab initio investigation of majorite and pyrope garnets: Lattice dynamics and vibrational spectra De La Pierre, Marco Belmonte, D. A detailed ab initio quantum-mechanical characterization is presented of the vibrational properties of pyrope and majorite garnets, using the hybrid B3LYP functional and large all electron Gaussian type basis sets. Discussed quantities include infrared (both TO and LO) and Raman frequencies, normal mode coordinates, spectroscopic intensities, mode Grüneisen parameters, isotopic substitution, and infrared and Raman spectra. Comparison with data available in the literature demonstrates the accuracy of the adopted method. Main spectral features of the two garnets are interpreted in terms of either symmetry analysis or structural contributions to the vibrational modes. Missing peaks in the experiments are discussed in light of the simulated spectra. The present high-quality vibrational data can be used to compute thermal expansivities at high-pressure and high-temperature conditions. Calculated values for majorite at the bottom of the mantle transition zone (aV = 2.2 × 10-5 K-1 at T = 1500 K and P = 20 GPa) turn out to be sensibly greater (up to three times) than those currently adopted in geophysical thermodynamic databases, thus calling for a careful revision of the numerical models for thermo-chemical convection of the Earth’s mantle 2016 Journal Article http://hdl.handle.net/20.500.11937/33346 10.2138/am-2016-5382 Mineralogical Society of America restricted
spellingShingle De La Pierre, Marco
Belmonte, D.
Ab initio investigation of majorite and pyrope garnets: Lattice dynamics and vibrational spectra
title Ab initio investigation of majorite and pyrope garnets: Lattice dynamics and vibrational spectra
title_full Ab initio investigation of majorite and pyrope garnets: Lattice dynamics and vibrational spectra
title_fullStr Ab initio investigation of majorite and pyrope garnets: Lattice dynamics and vibrational spectra
title_full_unstemmed Ab initio investigation of majorite and pyrope garnets: Lattice dynamics and vibrational spectra
title_short Ab initio investigation of majorite and pyrope garnets: Lattice dynamics and vibrational spectra
title_sort ab initio investigation of majorite and pyrope garnets: lattice dynamics and vibrational spectra
url http://hdl.handle.net/20.500.11937/33346