Item


Finite field treatment of vibrational polarizabilities and hyperpolarizabilities: on the role of the Eckart conditions, their implementation, and their use in characterizing key vibrations

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

© Journal of Chemical Physics, 1999, vol. 111, núm. 3, p. 875-884

American Institute of Physics

Author: Luis Luis, Josep Maria
Duran i Portas, Miquel
Andrés, José Luís
Champagne, Benoît
Kirtman, Bernard
Date: 1999
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
Format: application/pdf
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
ISSN: 0021-9606 (versió paper)
1089-7690 (versió electrònica)
Document access: http://hdl.handle.net/10256/3224
Language: eng
Publisher: American Institute of Physics
Collection: Reproducció digital del document publicat a: http://dx.doi.org/10.1063/1.479373
Articles publicats (D-Q)
Is part of: © Journal of Chemical Physics, 1999, vol. 111, núm. 3, p. 875-884
Rights: Tots els drets reservats
Subject: Òptica no lineal
Polarització (Electricitat)
Nonlinear optics
Polarization (Electricity)
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
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

Subjects

Authors