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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

Autor: Luis Luis, Josep Maria
Duran i Portas, Miquel
Andrés, José Luís
Champagne, Benoît
Kirtman, Bernard
Data: 1999
Resum: 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
Cita: 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)
Accés al document: http://hdl.handle.net/10256/3224
Llenguatge: eng
Editor: American Institute of Physics
Col·lecció: Reproducció digital del document publicat a: http://dx.doi.org/10.1063/1.479373
Articles publicats (D-Q)
És part de: © Journal of Chemical Physics, 1999, vol. 111, núm. 3, p. 875-884
Drets: Tots els drets reservats
Matèria: Òptica no lineal
Polarització (Electricitat)
Nonlinear optics
Polarization (Electricity)
Títol: Finite field treatment of vibrational polarizabilities and hyperpolarizabilities: on the role of the Eckart conditions, their implementation, and their use in characterizing key vibrations
Tipus: info:eu-repo/semantics/article
Repositori: DUGiDocs

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