Electric multipole moment, dipole and quadrupole (hyper)polarizability derivatives for HF ( X1Σ+)

Abstract

We report accurate values for the electric properties and property derivatives of hydrogen fluoride. Our approach is based on finite-field Møller–Plesset perturbation theory and coupled cluster calculations performed with large, carefully optimised basis sets of gaussian-type functions. All basis sets used in this study are of well-evidenced near-Hartree–Fock quality for all properties of interest. Our best values are obtained from CCSD(T) calculations (all electrons correlated) with a (16s11p8d4f/10s6p3d2f) basis set at the experimental bond length R e=1.7328 a 0: dipole, μ=0.7043 ea 0, quadrupole, Θ=1.71 ea 0 2, octopole, Ω=2.50ea 0 3, and hexadecapole, Φ=4.83 ea 0 3, moment, mean α ̄ =5.60 and anisotropy, Δ α=1.14 e 2 a 0 2 E h −1 of the dipole polarizability, mean first, β ̄ =−7.4e 3a 0 3E h −2 and second, γ ̄ =512e 4a 0 4E h −3 hyperpolarizability, mean quadrupole, C ̄ =10.61e 2a 0 4E h −1 polarizability. The R-dependence around R e is obtained for all properties. At the CCSD(T)/[9s6p5d4f/6s4p3d1f] level of theory (all electrons correlated) α ̄ and Δ α vary around R e as α ̄ (R)/e 2a 0 2E h −1=5.66+2.92(R−R e )+1.10(R−R e ) 2+0.24(R−R e ) 3−0.01(R−R e ) 4 Δα(R)/e 2a 0 2E h −1=1.12+4.30(R−R e )+2.97(R−R e ) 2+0.78(R−R e ) 3+0.07(R−R e ) 4 For the mean higher polarizabilities we report CCSD(T)/[9s6p5d4f/6s4p3d1f] (all electrons correlated) first derivatives, d β ̄ dR e =12.4e 3a 0 2E h −2, d γ ̄ dR e =437e 4a 0 3E h −3 and d C ̄ dR e =8.02e 2a 0 3E h −1. At the MP2/[9s6p5d4f/6s4p3d1f] level of theory, the dipole–quadrupole ( A α, βγ ) polarizability varies around R e as: A z,zz(R)/e 2a 0 3E h −1=4.33+10.83(R−R e )+8.69(R−R e ) 2+2.99(R−R e ) 3+0.19(R−R e ) 4 A x,zx(R)/e 2a 0 3E h −1=1.32+2.27(R−R e )+1.30(R−R e ) 2+0.27(R−R e ) 3+0.07(R−R e ) 4