Theoretical analysis of the electronic structure and molecular properties of the alkali halides. I. Lithium chloride

Abstract

Results of a theoretical investigation of the electronic structure of LiCl within the SCF-LCAO-MO framework are discussed, giving special emphasis to the evaluation of various molecular properties. Computed values (followed by experimental values in parentheses) for the total energy E, equilibrium separation Re, spectroscopic constants ωe, ωexe, and Be, and the dipole moment μ, are E=-467.05466 a.u., Re=3.825 a.u. (3.819 a.u.), ωe=671.5 cm-1 (641 cm-1), ωexe=4.67 cm-1 (4.2 cm-1), Be=0.704 cm-1 (0.706 cm-1), μυ=7.2182+0.0753(υ+1/2)+0.0002(υ+1/2)2, and μυ(exptl)=7.0853+0.0864(υ+1/2)+0.0O06(υ+1/2) 2. Computed dissociation energies, coupled with relativistic and correlation energy contributions estimated from atomic data, result in a value for De of 0.174 a.u. as compared with the experimental value of 0.178 a.u. Computed values for the field gradients at the nuclei have been combined with experimental values of the quadrupole coupling constants to yield, for the nuclear quadrupole moments of lithium and chlorine, QLi=-0. 050×10-24cm2, Q37Cl=-0. 084×10-24cm2, Q35Cl=-0. 106×10-24cm2.