Variational calculation of vibrational linear and nonlinear optical properties.
A variational approach for reliably calculating vibrational linear and nonlinear optical properties of molecules with large electrical and/or mechanical anharmonicity is introduced. This approach utilizes a self-consistent solution of the vibrational Schrodinger equation for the complete field-dependent potential-energy surface and, then, adds higher-level vibrational correlation corrections as desired. An initial application is made to static properties for three molecules of widely varying anharmonicity using the lowest-level vibrational correlation treatment (i.e., vibrational Møller-Plesset perturbation theory). Our results indicate when the conventional Bishop-Kirtman perturbation method can be expected to break down and when high-level vibrational correlation methods are likely to be required. Future improvements and extensions are discussed.
Torrent-Sucarrat
Miquel
M
Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA.
Luis
Josep M
JM
Kirtman
Bernard
B
D000465:Algorithms; D003198:Computer Simulation; D007536:Isomerism; D016014:Linear Models; D008956:Models, Chemical; D008958:Models, Molecular; D017711:Nonlinear Dynamics; D055095:Optics and Photonics; D014732:Vibration