Title: A new dipole-free sum-over-states expression for the second hyperpolarizability
Authors: Perez-Moreno, Javier ×
Clays, Koen
Kuzyk, Mark G #
Issue Date: Feb-2008
Publisher: Amer inst physics
Series Title: Journal of Chemical Physics vol:128 issue:8
Article number: 084109
Abstract: The generalized Thomas-Kuhn sum rules are used to eliminate the explicit dependence on dipolar terms in the traditional sum-over-states (SOS) expression for the second hyperpolarizability to derive a new, yet equivalent, SOS expression. This new dipole-free expression may be better suited to study the second hyperpolarizability of nondipolar systems such as quadrupolar, octupolar, and dodecapolar structures. The two expressions lead to the same fundamental limits of the off-resonance second hyperpolarizability; and when applied to a particle in a box and a clipped harmonic oscillator, have the same frequency dependence. We propose that the new dipole-free equation, when used in conjunction with the standard SOS expression, can be used to develop a three-state model of the dispersion of the third-order susceptibility that can be applied to molecules in cases where normally many more states would have been required. Furthermore, a comparison between the two expressions can be used as a convergence test of molecular orbital calculations when applied to the second hyperpolarizability. (c) 2008 American Institute of Physics.
ISSN: 0021-9606
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Molecular Imaging and Photonics
× corresponding author
# (joint) last author

Files in This Item:

There are no files associated with this item.

Request a copy


All items in Lirias are protected by copyright, with all rights reserved.

© Web of science