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Ab initio vibrational spectra and dielectric properties of carbonates: magnesite, calcite and dolomite

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Abstract

The equilibrium geometry, the Raman and IR vibrational spectra at the Γ point, TO–LO splitting, IR intensities, Born and dielectric tensors of magnesite MgCO3, dolomite MgCa(CO3)2 and calcite CaCO3 have been calculated with the periodic ab initio program CRYSTAL, by using an all-electron gaussian type basis set and the B3LYP hamiltonian. LO (longitudinal-optical) modes are computed by correcting the dynamical matrix through Born charges and high frequency dielectric tensors obtained from well localized Wannier functions and a saw-tooth computational scheme. The mean absolute difference between calculated and experimental frequencies (IR TO and LO and RAMAN) is as small as 6.9 cm−1 for magnesite, 7.7 cm−1 for dolomite and 8.5 cm−1 for calcite. Calculated IR intensities are in semiquantitative agreement with experiment. The modes of the three compounds are compared through graphical animation available on the CRYSTAL web-site.

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Authors and Affiliations

  1. Dipartimento di Chimica IFM, Università di Torino and NIS (Nanostructured Interfaces and Surfaces), Via P. Giuria 5, 10125, Torino, Italy

    L. Valenzano

  2. Laboratoire de Pétrologie, Modélisation de Matériaux et Processus, UMR 7160, Université Pierre et Marie Curie, 4 Place Jussieu, 75232, Paris cedex 05, France

    Y. Noël

  3. Dipartimento di Scienze e Tecnologie Avanzate, Università del Piemonte Orientale, Via Bellini 25/G, 15100, Alessandria, Italy

    R. Orlando

  4. Facultad de Ciencias, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, Col Chamilpa, 62210, Cuernavaca (MOR), Mexico

    C. M. Zicovich-Wilson

  5. Dipartimento di Chimica IFM, Università di Torino and NIS (Nanostructured Interfaces and Surfaces), Via P. Giuria 7, 10125, Torino, Italy

    M. Ferrero

  6. Dipartimento di Chimica IFM, Università di Torino and NIS (Nanostructured Interfaces and Surfaces), Centre of Excellence, Via P. Giuria 7, 10125, Torino, Italy

    R. Dovesi

Authors
  1. L. Valenzano
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  2. Y. Noël
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  3. R. Orlando
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  4. C. M. Zicovich-Wilson
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  5. M. Ferrero
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  6. R. Dovesi
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Correspondence to R. Dovesi.

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Valenzano, L., Noël, Y., Orlando, R. et al. Ab initio vibrational spectra and dielectric properties of carbonates: magnesite, calcite and dolomite. Theor Chem Account 117, 991–1000 (2007). https://doi.org/10.1007/s00214-006-0213-2

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  • DOI: https://doi.org/10.1007/s00214-006-0213-2

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