Accurate STF HF wave functions from B to Ca and accurate STF HF wave functions for N2 and P2

Abstract

Accurate Slater type function (STF) Hartree–Fock (HF) wave functions are calculated from B to Ca. The STF’s have a form of rne−γr and power (n) of r is carefully chosen. The total atomic energies agree with those of numerical HF (NHF) within the errors of 3×10−6 and 1×10−5 a.u. for B to Ne and for Na to Ca, respectively. It will be also shown that for the N2 molecule, the present atomic STF HF set augmented with four 3d, three 4f, and one 5g STF polarization functions gives the total energy of −108.9937 a.u. at R=2.068 a.u. which is quite close to that of NHF, −108.9939 a.u. It is found that one 5g type polarization function is indispensable for getting the accurate HF value. The near HF wave function for the P2 molecule, which has the same quality as that of N2, will be also shown in the present work. The basis sets for N2 are applied to configuration interaction calculations in order to see the role of the polarization functions on the correlation effects.