Item


A full dimensionality approach to evaluate the nonlinear optical properties of molecules with large amplitude anharmonic tunneling motions

Previously, a reduced dimensionality approach was used to determine the vibrational contribution to nonlinear optical properties for molecules with large amplitude anharmonic modes that takes into account tunneling between potential wells (Luis, J. M.; Reis, H.; Papadopoulos, M. G.; Kirtman, B. J. Chem. Phys.2009, 131, 034116). Here, the treatment is extended, again using ammonia as an example, to include the remaining modes at several approximate levels. It is shown that this extension is essential to obtaining the correct results. Our new approach fully accounts for tunneling and avoids possible convergence problems associated with the normal coordinate expansion of the potential energy surface in a single-well treatment. For accurate numerical values, a good treatment of electron correlation is required along with a flexible basis set including diffuse functions

The following organizations are thanked for financial support: the European Union Seventh Framework Programme (FP7-REGPOT-2009-1, Grant N. 245866), the Spanish Ministerio de Ciencia e Innovacion (MICINN, CTQ2011-23156/BQU), and the DIUE of the Generalitat de Catalunya (2009SGR637 and Xarxa de Referencia en Quimica Teorica i Computacional). M.G.-B. thanks the Spanish MEC for a doctoral fellowship no. AP2010-2517. Support for the research of M.S. was received through the ICREA Academia 2009 prize for excellence in research funded by the DIUE of the Generalitat de Catalunya. Financial support from MICINN and the FEDER fund (European Fund for Regional Development) was provided by grant UNGI08-4E-003

© Journal of Chemical Theory and Computation, 2013, vol. 9, núm. 1, p. 520-532

American Chemical Society (ACS)

Author: Garcia Borràs, Marc
Solà i Puig, Miquel
Lauvergnat, David
Reis, Heribert C.
Luis Luis, Josep Maria
Kirtman, Bernard
Date: 2013
Abstract: Previously, a reduced dimensionality approach was used to determine the vibrational contribution to nonlinear optical properties for molecules with large amplitude anharmonic modes that takes into account tunneling between potential wells (Luis, J. M.; Reis, H.; Papadopoulos, M. G.; Kirtman, B. J. Chem. Phys.2009, 131, 034116). Here, the treatment is extended, again using ammonia as an example, to include the remaining modes at several approximate levels. It is shown that this extension is essential to obtaining the correct results. Our new approach fully accounts for tunneling and avoids possible convergence problems associated with the normal coordinate expansion of the potential energy surface in a single-well treatment. For accurate numerical values, a good treatment of electron correlation is required along with a flexible basis set including diffuse functions
The following organizations are thanked for financial support: the European Union Seventh Framework Programme (FP7-REGPOT-2009-1, Grant N. 245866), the Spanish Ministerio de Ciencia e Innovacion (MICINN, CTQ2011-23156/BQU), and the DIUE of the Generalitat de Catalunya (2009SGR637 and Xarxa de Referencia en Quimica Teorica i Computacional). M.G.-B. thanks the Spanish MEC for a doctoral fellowship no. AP2010-2517. Support for the research of M.S. was received through the ICREA Academia 2009 prize for excellence in research funded by the DIUE of the Generalitat de Catalunya. Financial support from MICINN and the FEDER fund (European Fund for Regional Development) was provided by grant UNGI08-4E-003
Format: application/pdf
ISSN: 1549-9618 (versió paper)
1549-9626 (versió electrònica)
Document access: http://hdl.handle.net/10256/11406
Language: eng
Publisher: American Chemical Society (ACS)
Collection: MICINN/PN 2012-2014/CTQ2011-23156
AGAUR/2009-2014/2009 SGR-637
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/ct300805p
Articles publicats (D-Q)
Is part of: © Journal of Chemical Theory and Computation, 2013, vol. 9, núm. 1, p. 520-532
Rights: Tots els drets reservats
Subject: Dinàmica molecular
Molecular dynamics
Title: A full dimensionality approach to evaluate the nonlinear optical properties of molecules with large amplitude anharmonic tunneling motions
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

Subjects

Authors