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

摘要

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 dipole 3 -hyperpolarizability tensor arexpresed in a way with theirotational behavior unequivocaly defined. The sets of equations for determination of the rotationally adapted the vector (K=1) and the septor (K=3) hyperpolarizability components API i ) (R), are given. Spherical, symmetry adapted components of the vector and the septor part of the first dipole 3 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 Aa03 3)(R),A(321'3i(R), A/323'3) (R), A(3(5'3)(R), A0 '31 (R), A^343'3) (R), and A/345'3)(R)are computed and discussed. Good agreement is observed between long-rang analytical and ab initio numerical data for themultipolar-like CI hyperpolarizability components.