The Raman spectrum of CaCO3 polymorphs calcite and aragonite: A combined experimental and computational study

Powder and single crystal Raman spectra of the two most common phases of calcium carbonate are calculated with ab initio techniques (using a “hybrid” functional and a Gaussian-type basis set) and measured both at 80 K and room temperature. Frequencies of the Raman modes are in very good agreement be...

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Main Authors: De La Pierre, Marco, Carteret, C., Maschio, L., Andre, E., Orlando, R., Dovesi, R.
Format: Journal Article
Published: American Institute of Physics 2014
Subjects:
Online Access:http://hdl.handle.net/20.500.11937/26373
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author De La Pierre, Marco
Carteret, C.
Maschio, L.
Andre, E.
Orlando, R.
Dovesi, R.
author_facet De La Pierre, Marco
Carteret, C.
Maschio, L.
Andre, E.
Orlando, R.
Dovesi, R.
author_sort De La Pierre, Marco
building Curtin Institutional Repository
collection Online Access
description Powder and single crystal Raman spectra of the two most common phases of calcium carbonate are calculated with ab initio techniques (using a “hybrid” functional and a Gaussian-type basis set) and measured both at 80 K and room temperature. Frequencies of the Raman modes are in very good agreement between calculations and experiments: the mean absolute deviation at 80 K is 4 and 8 cm−1 for calcite and aragonite, respectively. As regards intensities, the agreement is in general good, although the computed values overestimate the measured ones in many cases. The combined analysis permits to identify almost all the fundamental experimental Raman peaks of the two compounds, with the exception of either modes with zero computed intensity or modes overlapping with more intense peaks. Additional peaks have been identified in both calcite and aragonite, which have been assigned to 18O satellite modes or overtones. The agreement between the computed and measured spectra is quite satisfactory; in particular, simulation permits to clearly distinguish between calcite and aragonite in the case of powder spectra, and among different polarization directions of each compound in the case of single crystal spectra.
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spelling curtin-20.500.11937-263732019-02-19T05:35:39Z The Raman spectrum of CaCO3 polymorphs calcite and aragonite: A combined experimental and computational study De La Pierre, Marco Carteret, C. Maschio, L. Andre, E. Orlando, R. Dovesi, R. quantum mechanical simulation Polarized Raman spectra single crystal polycrystalline powder ab initio Raman intensities calcium carbonate wavenumbers CRYSTAL code Powder and single crystal Raman spectra of the two most common phases of calcium carbonate are calculated with ab initio techniques (using a “hybrid” functional and a Gaussian-type basis set) and measured both at 80 K and room temperature. Frequencies of the Raman modes are in very good agreement between calculations and experiments: the mean absolute deviation at 80 K is 4 and 8 cm−1 for calcite and aragonite, respectively. As regards intensities, the agreement is in general good, although the computed values overestimate the measured ones in many cases. The combined analysis permits to identify almost all the fundamental experimental Raman peaks of the two compounds, with the exception of either modes with zero computed intensity or modes overlapping with more intense peaks. Additional peaks have been identified in both calcite and aragonite, which have been assigned to 18O satellite modes or overtones. The agreement between the computed and measured spectra is quite satisfactory; in particular, simulation permits to clearly distinguish between calcite and aragonite in the case of powder spectra, and among different polarization directions of each compound in the case of single crystal spectra. 2014 Journal Article http://hdl.handle.net/20.500.11937/26373 10.1063/1.4871900 American Institute of Physics fulltext
spellingShingle quantum mechanical simulation
Polarized Raman spectra
single crystal
polycrystalline powder
ab initio
Raman intensities
calcium carbonate
wavenumbers
CRYSTAL code
De La Pierre, Marco
Carteret, C.
Maschio, L.
Andre, E.
Orlando, R.
Dovesi, R.
The Raman spectrum of CaCO3 polymorphs calcite and aragonite: A combined experimental and computational study
title The Raman spectrum of CaCO3 polymorphs calcite and aragonite: A combined experimental and computational study
title_full The Raman spectrum of CaCO3 polymorphs calcite and aragonite: A combined experimental and computational study
title_fullStr The Raman spectrum of CaCO3 polymorphs calcite and aragonite: A combined experimental and computational study
title_full_unstemmed The Raman spectrum of CaCO3 polymorphs calcite and aragonite: A combined experimental and computational study
title_short The Raman spectrum of CaCO3 polymorphs calcite and aragonite: A combined experimental and computational study
title_sort raman spectrum of caco3 polymorphs calcite and aragonite: a combined experimental and computational study
topic quantum mechanical simulation
Polarized Raman spectra
single crystal
polycrystalline powder
ab initio
Raman intensities
calcium carbonate
wavenumbers
CRYSTAL code
url http://hdl.handle.net/20.500.11937/26373