Portal de Periódicos da CAPES

Gaussian basis sets which yield accurate Hartree—Fock electric moments and polarizabilities

1982; Elsevier BV; Volume: 89; Issue: 1-2 Linguagem: Inglês

10.1016/0166-1280(82)80164-4

1872-7999

Jeanne G. C. M. van Duijneveldt-van de Rijdt, F. B. van Duijneveldt,

Spectroscopy and Quantum Chemical Studies

Calculated dipole, quadrupole and octopole moments and dipole polarizabilities are reported for H2, CH4, NH3, H2O, HF, HCN, H2CO, H3CF and HCOOH in the Hartree—Fock approximation. Nine different basis sets are employed, ranging from a minimal basis to a large triply polarized basis. It is argued that in order to achieve an accuracy of 0.001 hartree in intermolecular interaction energies, the errors in computed monomer moments should be less than 0.03, 0.15 and 0.75 au for μ, θ and Ω, respectively, while α should be correct to within 2 a03. Measured by these standards, the DZPP and larger sets provide results close to the Hartree—Fock limit, but the commonly used energy-optimized DZP basis proves unsatisfactory. An alternative moment-optimized DZP′ basis is proposed which is shown to be the smallest basis yielding results acceptably close to the Hartree—Fock limit. Vibrational corrections are estimated for the hydrides and turn out to be small. Comparison w ith experiment then shows that correlation corrections are important, especially for μ and α. Details on contraction schemes and standard scale factors for the different basis sets are given in the Appendix.