One-Electron Spin-Orbit Contribution by Effective Nuclear Charges

Effective nuclear charges of the main group elements from the second up to the fifth row have been developed for the one-electron part of the spin-orbit (SO) coupling Hamiltonian. These parameters. suitable to be used for SO calculations of large molecular systems, provide a useful and remarkably good approximation to the full SO Hamiltonian. We have derived atomic effective nuclear charges by fitting procedure. Computed fine-structure splitting (FSS) of the doublet and triplet II states of AH species (A is one of the abovementioned elements) have been chosen for this purpose. We have adopted the noniterative scheme, previously reported, according to which SO contributions can be calculated through direct coupling between the II states. The latter have been optimized at B3LYP level using DZVP basis sets. As surrogates for a large number of possible applications, we have widely employed the empirical parameters to compute II-FSSs of diatomic species for which experimental data are available. (C) 2008 Wiley Periodicals, Inc. J Comput Chem 30: 832-839, 2009