Journal of Chemical Physics, Vol.100, No.6, 4417-4431, 1994
The Calculation of Molecular Response Properties Using Perturbed Spin-Coupled Wave-Functions .2. Polarizability and Magnetic-Susceptibility of H-2 and Lih as Functions of Internuclear Distance
The perturbed spin-coupled formalism of the previous paper is applied to the calculation of the polarizabilities and magnetic susceptibilities of H-2 and LiH. These are the first applications of the theory and as such much attention is paid to the choice of basis set, particularly as a function of internuclear distance. For H-2, the results can be compared with the accurate calculations of Rychlewski [Mol. Phys. 41, 833 (1980)] and of Rychlewski and Raynes [Mol. Phys. 41, 843 (1980)]. The agreement with these is good, provided that the basis set is adequate. For LiH, there has, to our knowledge, not been any calculation of these properties as a function of R. However the value of alpha at large R is in excellent agreement with the value of alpha(Li)+alpha(H). A remarkable feature in LiH is that the value of alpha(zz) at similar to 7a(0) is ten times that for R=R(e). In general we find that the determination of magnetic susceptibilities as a function of R forms a very severe test of the completeness of the basis set.
Keywords:NMR CHEMICAL-SHIFTS;ORBITAL METHODS;BASIS-SETS;ELECTRIC POLARIZABILITIES;ISOTOPIC-SUBSTITUTION;ACCURATE CALCULATION;HYDROGEN MOLECULE;SCF CALCULATIONS;LITHIUM HYDRIDE;DIPOLE-MOMENT