Evaluation of the LCAO Hartree-Fock-Slater method: Applications to transition-metal complexes

The LCAO Hartree-Fock-Slater method is evaluated by comparing results of this method obtained in an accurate STO basis for a series of small diatomic molecules with experimental data and with results of Hartree-Fock calculations. It is found that the Xα potential, if applied with the same care as the Hartree-Fock potential (i.e., comparable basis set quality, etc.), leads to results that are at least as close to experiment as Hartree-Fock results. Because the HFS method is relatively fast, it can be used easily for calculations on transition-metal complexes, even in calculations with STO basis sets of double-zeta quality or better. Calculated ionization energies, core-electron energy shifts, spectroscopic term energies, infrared and Raman data, and electronic structures calculated for transition-metal complexes compare excellently with experiment.