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Erba A, Maul J, Ferrabone M, et al. Anharmonic Vibrational States of Solids from DFT Calculations. Part II: Implementation of the VSCF and VCI Methods. J Chem Theory Comput. 2019;15(6):3766-3777doi: 10.1021/acs.jctc.9b00294.
Erba, A., Maul, J., Ferrabone, M., Dovesi, R., Rérat, M., & Carbonnière, P. (2019). Anharmonic Vibrational States of Solids from DFT Calculations. Part II: Implementation of the VSCF and VCI Methods. Journal of chemical theory and computation, 15(6), 3766-3777. https://doi.org/10.1021/acs.jctc.9b00294
Erba, Alessandro, et al. "Anharmonic Vibrational States of Solids from DFT Calculations. Part II: Implementation of the VSCF and VCI Methods." Journal of chemical theory and computation vol. 15,6 (2019): 3766-3777. doi: https://doi.org/10.1021/acs.jctc.9b00294
Erba A, Maul J, Ferrabone M, Dovesi R, Rérat M, Carbonnière P. Anharmonic Vibrational States of Solids from DFT Calculations. Part II: Implementation of the VSCF and VCI Methods. J Chem Theory Comput. 2019 Jun 11;15(6):3766-3777. doi: 10.1021/acs.jctc.9b00294. Epub 2019 May 28. PMID: 31038948.
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J Chem Theory Comput. 2019 Jun 11;15(6):3766-3777. doi: 10.1021/acs.jctc.9b00294. Epub 2019 May 28.

Anharmonic Vibrational States of Solids from DFT Calculations. Part II: Implementation of the VSCF and VCI Methods.

Journal of chemical theory and computation

Alessandro Erba, Jefferson Maul, Matteo Ferrabone, Roberto Dovesi, Michel Rérat, Philippe Carbonnière

Affiliations

  1. Dipartimento di Chimica , Universitá di Torino , via Giuria 5 , 10125 Torino , Italy.
  2. IPREM , Université de Pau et des Pays de l'Adour, IPREM-CAPT UMR CNRS 5254, Hélioparc Pau Pyrénées , 2 avenue du Président Angot , 64053 PAU CEDEX 9, Pau , France.

PMID: 31038948 DOI: 10.1021/acs.jctc.9b00294

Abstract

Two methods are implemented in the Crystal program for the calculation of anharmonic vibrational states of solids: the vibrational self-consistent field (VSCF) and the vibrational configuration-interaction (VCI). While the former is a mean-field approach, where each vibrational mode interacts with the average potential of the others, the latter allows for an explicit and complete account of mode-mode correlation. Both schemes are based on the representation of the adiabatic potential energy surface (PES) discussed in Part I, where the PES is expanded in a Taylor's series so as to include up to cubic and quartic terms. The VSCF and VCI methods are formally presented and their numerical parameters discussed. In particular, the convergence of computed anharmonic vibrational states, within the VCI method, is investigated as a function of the truncation of the expansion of the nuclear wave function. The correctness and effectiveness of the implementation is discussed by comparing with available theoretical and experimental data on both molecular and periodic systems. The effect of the adopted basis set and exchange-correlation functional in the description of the PES on computed anharmonic vibrational states is also addressed.

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