Finite-perturbation SCF valence-shell calculations of molecular polarizability and hyperpolarizability components

✍ Scribed by N.S. Hush; M.L. Williams

• Publisher: Elsevier Science
• Year: 1970
• Tongue: English
• Weight: 460 KB
• Volume: 5
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(70)85121-1

✦ Synopsis

A finite-perturbation method is used for obtaining approximate valence-shell eigenfunctions of molccules interacting with uniform static electric fields within the frame\vork of unrestricted oper;-shell CNDO/II theory. For a series of axially symmetric molecules, components of the polarizability tensor have been calculated. It is found that although the average polarizabilities (r are underpredicted, the anisotropies (Y,, -aI are remarkably well predicted by this method. Some calculation of hyperpolarizabilities &JS~ are also reported: these cannot yet be compared with experiment, but the result for CO is close to that of an ab initio calculation of iCIcLean and Yoshirnine. The polarizability results are also compared with infinitesimal-perturbation CXDO/II calculations of Davies.