Anatomy of relativistic energy corrections in light molecular systems

Relativistic energy corrections which arise from the use of the Dirac-Coulomb Hamiltonian, and the Gaunt and Breit interaction operators, plus Lamb-shift effects have been determined for the global minima of the ground electronic states of C₂H₆, NH₃, H₂O, H,C,N], HNCO, HCOOH, SiC₂, SiH^? ₃, and H₂S, and for barrier characteristics for these molecular systems (inversion barrier of NH₃ and SiH^? ₃, barrier to linearity of H₂O, H₂S, and HNCO, rotational barrier of C₂H₆, difference between conformations of HCOOH (Z/E) and SiC₂ (linear/T-shaped), and isomerization barrier of HCN/HNC). The relativistic calculations performed at the Hartree-Fock and the highly correlated CCSD(T) levels employed a wide variety of basis sets. Comparison of the perturbational and the four-component fully variational results indicate that the Coulomb-Pauli Hamiltonian and the lowest order Hamiltonian of direct perturbation theory (DPT(2)) are highly successful for treating the relativistic energy effects in light molecular systems both at a single point on the potential energy hypersurface and along the surface. Electron correlation contributions to the relativistic corrections are relatively small for the systems studied, and are comparable with the 2-electron Darwin correction. Corrections beyond the Dirac-Coulomb treatment are usually rather small, but may become important for high accuracy ab initio calculations.