Polarization correction to the electrostatic potential at the CNDO and the ab initio level. Influence of the basis set expansion

The influence of the basis set on the electrostatic potential corrected for polarization has been studied for H2S, CH3SH and COHCH2SH. The position and deepness of the minima and the height of the barrier between symmetric minima is discussed at both the deorthogonalized CNDO/2 and ab initio levels within STO-3G, 3-21G, 4-31G, 6-31G and 6-311G basis sets. The calculation of the electrostatic potential and corrected one using CNDO deorthogonalized coefficients including 3d orbitals has been applied at the first time on sulfur-containing molecules. The influence of polarization and diffuse functions has also been analysed and the incidence of the polarization correction on the relative proton affinity in NH2(CH2)3NHCH3 and in the adenine molecule has been investigated at the CNDO and ab initio levels. At both levels, the relative proton affinity of several basic sites in the same molecule can be qualitatively expressed without inclusion of the polarization correction except in the case of substituted amines.