A full dimensionality approach to evaluate the nonlinear optical properties of molecules with large amplitude anharmonic tunneling motions
dc.contributor.author
dc.date.accessioned
2015-10-28T12:16:43Z
dc.date.available
2015-10-28T12:16:43Z
dc.date.issued
2013
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1549-9618
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dc.description.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
dc.description.sponsorship
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
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
dc.relation
info:eu-repo/grantAgreement/MICINN//CTQ2011-23156/ES/AVANCES EN CATALISIS Y AROMATICIDAD/
AGAUR/2009-2014/2009 SGR-637
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Reproducció digital del document publicat a: http://dx.doi.org/10.1021/ct300805p
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© Journal of Chemical Theory and Computation, 2013, vol. 9, núm. 1, p. 520-532
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Articles publicats (D-Q)
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Tots els drets reservats
dc.subject
dc.title
A full dimensionality approach to evaluate the nonlinear optical properties of molecules with large amplitude anharmonic tunneling motions
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/embargoedAccess
dc.embargo.terms
Cap
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2026-01-01
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
017378
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dc.relation.ProjectAcronym
dc.identifier.eissn
1549-9626