The Septor Part of a Linear Molecule—Atom Collision-Induced Hyperpolarizability

Abstract

A method for the computation of spherical, rotationally adapted components of the collision‐induced (CI) hyperpolarizability tensor, needed for spectroscopic line shape analysis, is presented. Components of the CI dipole3‐hyperpolarizability tensor are expressed in a way with their rotational behavior unequivocally defined. The sets of equations for determination of the rotationally adapted the vector (K = 1) and the septor (K = 3) hyperpolarizability components ΔβλL(s,K)(R), are given. Spherical, symmetry adapted components of the vector and the septor part of the first dipole3 hyperpolarizability tensor are computed. Results are applied to the case of H2‐Ar pair. The septor part is discussed in detail. The seven septor rotationally adapted components Δβ03(s,3)(R), Δβ21(s,3)(R), Δβ23(s,3)(R), Δβ25(s,3)(R), Δβ41(s,3)(R), Δβ43(s,3)(R), and Δβ45(s,3)(R), are computed and discussed. Good agreement is observed between long‐rang analytical and ab initio numerical data for the multipolar‐like CI hyperpolarizability components.