The IR vibrational properties of six members of the garnet family: A quantum mechanical ab initio study
The IR vibrational properties and the corresponding reflectance spectra of the six most common members of the garnet family (pyrope Mg3Al2Si3O12, almandine Fe3Al2Si3O12, spessartine Mn3Al2Si3O12, grossular Ca3Al2Si3O12, uvarovite Ca3Cr2Si3O12, and andradite Ca3Fe2Si3O12) were simulated at the ab ini...
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| Format: | Journal Article |
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Mineralogical Society of America
2011
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| Online Access: | http://hdl.handle.net/20.500.11937/16869 |
| _version_ | 1848749300614430720 |
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| author | Dovesi, R. De La Pierre, Marco Ferrari, A. Pascale, F. Maschio, L. Zicovich-Wilson, C. |
| author_facet | Dovesi, R. De La Pierre, Marco Ferrari, A. Pascale, F. Maschio, L. Zicovich-Wilson, C. |
| author_sort | Dovesi, R. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | The IR vibrational properties and the corresponding reflectance spectra of the six most common members of the garnet family (pyrope Mg3Al2Si3O12, almandine Fe3Al2Si3O12, spessartine Mn3Al2Si3O12, grossular Ca3Al2Si3O12, uvarovite Ca3Cr2Si3O12, and andradite Ca3Fe2Si3O12) were simulated at the ab initio level with the CRYSTAL09 code by using a large all-electron Gaussian-type basis set and the B3LYP hybrid functional. The 17 IR active F1u transverse optical (TO) and longitudinal optical (LO) frequencies, the oscillator strengths, the high frequency and static dielectric constants, and the reflectance spectrum were computed. The agreement with experiments for the TO and LO peaks is always excellent, the mean absolute difference for the whole set of data (overall 178 peaks) being 5 cm−1. Oscillator strengths, calculated from the mass-weighted effective Born charges, are found in semi-quantitative agreement with the experimental data. The reflectance spectra, simulated through the classical dispersion relation, reproduce the experimental curves extremely well. The availability of the full set of simulated frequencies and intensities, obtained by using uniform computational tools (computer code, variational basis sets, density functional), permits the establishment of correlations between IR wavenumbers and structural features suggested, but only partially documented, in the past. |
| first_indexed | 2025-11-14T07:18:45Z |
| format | Journal Article |
| id | curtin-20.500.11937-16869 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T07:18:45Z |
| publishDate | 2011 |
| publisher | Mineralogical Society of America |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | curtin-20.500.11937-168692017-10-02T02:28:15Z The IR vibrational properties of six members of the garnet family: A quantum mechanical ab initio study Dovesi, R. De La Pierre, Marco Ferrari, A. Pascale, F. Maschio, L. Zicovich-Wilson, C. reflectance spectrum B3LYP functional all-electron gaussian basis sets Garnet IR intensities IR frequencies CRYSTAL code ab initio calculations The IR vibrational properties and the corresponding reflectance spectra of the six most common members of the garnet family (pyrope Mg3Al2Si3O12, almandine Fe3Al2Si3O12, spessartine Mn3Al2Si3O12, grossular Ca3Al2Si3O12, uvarovite Ca3Cr2Si3O12, and andradite Ca3Fe2Si3O12) were simulated at the ab initio level with the CRYSTAL09 code by using a large all-electron Gaussian-type basis set and the B3LYP hybrid functional. The 17 IR active F1u transverse optical (TO) and longitudinal optical (LO) frequencies, the oscillator strengths, the high frequency and static dielectric constants, and the reflectance spectrum were computed. The agreement with experiments for the TO and LO peaks is always excellent, the mean absolute difference for the whole set of data (overall 178 peaks) being 5 cm−1. Oscillator strengths, calculated from the mass-weighted effective Born charges, are found in semi-quantitative agreement with the experimental data. The reflectance spectra, simulated through the classical dispersion relation, reproduce the experimental curves extremely well. The availability of the full set of simulated frequencies and intensities, obtained by using uniform computational tools (computer code, variational basis sets, density functional), permits the establishment of correlations between IR wavenumbers and structural features suggested, but only partially documented, in the past. 2011 Journal Article http://hdl.handle.net/20.500.11937/16869 10.2138/am.2011.3804 Mineralogical Society of America fulltext |
| spellingShingle | reflectance spectrum B3LYP functional all-electron gaussian basis sets Garnet IR intensities IR frequencies CRYSTAL code ab initio calculations Dovesi, R. De La Pierre, Marco Ferrari, A. Pascale, F. Maschio, L. Zicovich-Wilson, C. The IR vibrational properties of six members of the garnet family: A quantum mechanical ab initio study |
| title | The IR vibrational properties of six members of the garnet family: A quantum mechanical ab initio study |
| title_full | The IR vibrational properties of six members of the garnet family: A quantum mechanical ab initio study |
| title_fullStr | The IR vibrational properties of six members of the garnet family: A quantum mechanical ab initio study |
| title_full_unstemmed | The IR vibrational properties of six members of the garnet family: A quantum mechanical ab initio study |
| title_short | The IR vibrational properties of six members of the garnet family: A quantum mechanical ab initio study |
| title_sort | ir vibrational properties of six members of the garnet family: a quantum mechanical ab initio study |
| topic | reflectance spectrum B3LYP functional all-electron gaussian basis sets Garnet IR intensities IR frequencies CRYSTAL code ab initio calculations |
| url | http://hdl.handle.net/20.500.11937/16869 |