Theoretical analysis of the electronic structure and molecular properties of the alkali halides. II. Sodium fluoride

Abstract

Results of a recent theoretical investigation of the electronic structure of NaF within the SCF-LCAO-MO approximation are discussed, with special emphasis on molecular properties. Computed values (followed by experimental values in parenthesis) for the total energy, E, equilibrium separation, Re, spectroscopic constants, ωe, ωexe, and Be, and the dipole moment μ are E=-261.37849 a.u., R e=3.628 a.u. (3.639), ωe=558.3 cm-1 (536.1), ωexe=4.387 cm-1 (3.830), B e=0.439 cm-1 (0.437), μν=8.3365+0.0610 (ν+1/2)+0.0002(ν+1/2)2, and μν(exptl)=8. 1235+0.0644(ν+1/2)+0.0004(ν+1/2). The computed dissociation energy (D 6HF=0.112 a.u.) has been coupled with correlation and relativistic energy contributions (Decorr=0.067 a.u.; Derel=-0.002 a.u.) determined from atomic data, producing a net De=0.178 a.u. as compared with the experimental value of 0.182 a.u. By combining the computed field gradient, qNa=-0.3775 a.u., with experimental values for the nuclear quadrupole coupling constant, we have determined a value of 0.0951×10-24cm2 for the sodium nuclear quadrupole moment.