How large is the static electric (hyper)polarizability anisotropy in HXeI?

Abstract

An extensive conventional ab initio and density functional theory investigation reveals that HXeI is a polar molecule with large multipole moments and highly anisotropic (hyper)polarizability. At the CCSD(T) level of theory our best values for the mean (hyper)polarizability are alphae(2)a(0) (2)E(h) (-1)=101.46, betae(3)a(0) (3)E(h) (-2)=-850.7, and gammae(4)a(0) (4)E(h) (-3)=18.7x10(3). The corresponding anisotropies are Deltaalphae(2)a(0) (2)E(h) (-1)=119.66, Deltabetae(3)a(0) (3)E(h) (-2)=-2518.7, Delta(1)gammae(4)a(0) (4)E(h) (-3)=-249.1x10(3), and Delta(2)gammae(4)a(0) (4)E(h) (-3)=-99.6x10(3). The longitudinal components of the (hyper)polarizability are dominant. Our value for the anisotropy of the dipole polarizability is considerably larger than the recent empirical estimate of 22.9 e(2)a(0) (2)E(h) (-1) [N. H. Nahler et al., J. Chem. Phys. 119, 224 (2003)]. The results of the insertion of Xe into HI are quantified by the calculation of the differential (hyper)polarizability at the MP2 level of theory: alpha(diff) identical withalpha(HXeI)-alpha(HI)-alpha(Xe)=36.29 e(2)a(0) (2)E(h) (-1) and gamma(diff) identical with gamma(HXeI)-gamma(HI)-gamma(Xe)=18.1x10(3) e(4)a(0) (4)E(h) (-3).