Frequency-dependent hyperpolarizabilities in the coupled-cluster method: the Kerr effect for molecules

✍ Scribed by Hideo Sekino; Rodney J. Bartlett

• Publisher: Elsevier Science
• Year: 1995
• Tongue: English
• Weight: 467 KB
• Volume: 234
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(95)00007-q

✦ Synopsis

Introducing frequency dependence in the equation-of-motion coupled-cluster method, we evaluate the optical Kerr effect for butadiene and ammonia. This permits a critical evaluation of dispersion estimates via the uncorrelated time-dependent Hartree-Fock theory. The percentage dispersions are similar for low frequencies, but not for larger values. We also consider other dispersion estimates based upon a power series expansion in the frequency. This leads to a possible resolution of the observed discrepancy between correlated theory and experiment for butadiene. Augmented by vibrational corrections, we offer estimates for the experimentally unknown Kerr values for NH 3 and Call 6.