Finite field treatment of vibrational polarizabilities and hyperpolarizabilities: on the role of the Eckart conditions, their implementation, and their use in characterizing key vibrations
dc.contributor.author
dc.date.accessioned
2011-02-07T13:16:02Z
dc.date.available
2010-12-14T12:53:04Z
2011-02-07T13:16:02Z
dc.date.issued
1999
dc.identifier.citation
Luis, J.M., Duran, M., Andrés, J.L., Champagne, B., i Kirtman, B. (1999). Finite field treatment of vibrational polarizabilities and hyperpolarizabilities: On the role of the Eckart conditions, their implementation, and their use in characterizing key vibrations. Journal of Chemical Physics, 111 (3), 875-884. Recuperat 7 febrer 2011, a http://link.aip.org/link/JCPSA6/v111/i3/p875/s1
dc.identifier.issn
0021-9606
dc.identifier.uri
dc.description.abstract
In the finite field (FF) treatment of vibrational polarizabilities and hyperpolarizabilities, the field-free Eckart conditions must be enforced in order to prevent molecular reorientation during geometry optimization. These conditions are implemented for the first time. Our procedure facilities identification of field-induced internal coordinates that make the major contribution to the vibrational properties. Using only two of these coordinates, quantitative accuracy for nuclear relaxation polarizabilities and hyperpolarizabilities is achieved in π-conjugated systems. From these two coordinates a single most efficient natural conjugation coordinate (NCC) can be extracted. The limitations of this one coordinate approach are discussed. It is shown that the Eckart conditions can lead to an isotope effect that is comparable to the isotope effect on zero-point vibrational averaging, but with a different mass-dependence
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
American Institute of Physics
dc.relation.isformatof
Reproducció digital del document publicat a: http://dx.doi.org/10.1063/1.479373
dc.relation.ispartof
© Journal of Chemical Physics, 1999, vol. 111, núm. 3, p. 875-884
dc.relation.ispartofseries
Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.subject
dc.title
Finite field treatment of vibrational polarizabilities and hyperpolarizabilities: on the role of the Eckart conditions, their implementation, and their use in characterizing key vibrations
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.identifier.doi
dc.identifier.eissn
1089-7690