Kramers' restricted hartree—fock method for polyatomic molecules using ab initio relativistic effective core potentials with spin—orbit operators

✍ Scribed by Sang Yeon Lee; Yoon Sup Lee

• Publisher: John Wiley and Sons
• Year: 1992
• Tongue: English
• Weight: 655 KB
• Volume: 13
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.540130509

✦ Synopsis

A two-component Kramers' restricted Hartree-Fock method (KRHF') has been developed for the polyatomic molecules with closed shell configurations. The present KRHF program utilizes the relativistic effective core potentials with spin-orbit operators at the Hartree-Fock (HF') level and produces molecular spinors obeying the double group symmetry. The KRHF program enables the variational calculation of spin-orbit interactions at the HF level. KRHF calculations have been performed for the HX, X,, Z ( X , Y = I, Br), and CH31 molecules. It is demonstrated that the orbital energies from KRHF calculations are useful for the interpretation of spinorbit splittings in photoelectron spectra. In all molecules studied, bond lengths are only slightly expanded, harmonic vibrational frequencies are reduced, and bond energies are significantly decreased by the spinorbit interactions.