Spin-orbit effects on structures of closed-shell polyatomic molecules containing heavy atoms calculated by two-component Hartree-Fock method

Abstract

We have implemented geometry optimization using an analytic gradient to a two-component Kramers' restricted Hartree-Fock (KRHF) method for polyatomic molecules with closed-shell configurations, The KRHF method is a Hartree-Fock method based on relativistic effective core potentials with effective spin-orbit operators. The derivatives of spin-orbit integrals are obtained by numerical differentiation. Geometries for the various forms of polyatomic hydrides containing row 6 p-block elements are optimized with and without spin-orbit interactions. The structural changes due to spin-orbit interactions are small, but show definite trends, which correlate well with the p(1/2) spinor population. Atomization energies are reduced significantly by incorporating spin-orbit interactions for all molecules considered. The KRHF calculations of several methylhalides demonstrate that the spinor energies from the KRHF method can be useful for the interpretation of experimental photoelectron spectra of molecules exhibiting spin-orbit splittings. (C) 1998 John Wiley & Sons, Inc. J Comput Chem 19: 1526-1533, 1998.