Relativistic and correlation effects on molecular properties .2. The hydrogen halides HF, HCl, HBr, HI, and HAt

A benchmark study of a number of four-component relativistic correlation methods is presented. Bond lengths, harmonic frequencies, and dissociation energies of the molecules HF, HCl, HBr, HI, and HAt are calculated at various levels of theory, using both the Schrodinger and the Dirac-Coulomb-(Gaunt) Hamiltonian. The inclusion of relativity leads to a weakening of the bond, giving a decrease in the calculated harmonic frequencies and dissociation energies of the hydrogen halides. The effect on the bond length is small. These trends are explained by considering the relativistic change in hybridization induced by the spin-orbit coupling. (C) 1996 American Institute of Physics.