A. Nicklass et al., Convergence of Breit-Pauli spin-orbit matrix elements with basis set size and configuration interaction space: The halogen atoms F, Cl, and Br, J CHEM PHYS, 112(13), 2000, pp. 5624-5632
Systematic sequences of basis sets are used to calculate the spin-orbit spl
ittings of the halogen atoms F, Cl, and Br in the framework of first-order
perturbation theory with the Breit-Pauli operator and internally contracted
configuration interaction wave functions. The effects of both higher angul
ar momentum functions and the presence of tight functions are studied. By s
ystematically converging the one-particle basis set, an unambiguous evaluat
ion of the effects of correlating different numbers of electrons in the Cl
treatment is carried out. Correlation of the 2p-electrons in chlorine incre
ases the spin-orbit splitting by similar to 80 cm(-1), while in bromine we
observe incremental increases of 130, 145, and 93 cm(-1), when adding the 3
d, 3p, and 2p electrons to the set of explicitly correlated electrons, resp
ectively. For fluorine and chlorine the final basis set limit, all-electron
s correlated results match the experimentally observed spin-orbit splitting
s to within similar to 5 cm(-1), while for bromine the Breit-Pauli operator
underestimates the splitting by about 100 cm(-1). More extensive treatment
of electron correlation results in only a slight lowering of the spin-orbi
t matrix elements. Thus, the discrepancy for bromine is proposed to arise f
rom the nonrelativistic character of the underlying wave function. (C) 2000
American Institute of Physics. [S0021-9606(00)31413-1].