Velocity formulations for hyper-Rayleigh scattering optical activity spectroscopy: Addressing the origin-dependence problem

Abstract

The theory of hyper-Rayleigh scattering optical activity (HRS-OA) spectroscopy has previously been described within the length formulation of the pure electric-dipole and mixed (electric-dipole/magnetic-dipole and electric-dipole/electric-quadrupole) first hyperpolarizabilities required for the description of this process. In this study, we provide an alternative formulation of these pure and mixed hyperpolarizabilities. This new formulation made use of the velocity form of the electric-dipole and electric-quadrupole moment operators that enter into the quadratic response functions. A one-to-one correspondence is found for the gauge-origin shifts obtained in the two formulations. These relations ensure the origin-independence of the theory also for the velocity formulation. Furthermore, even though the basis set dependence of the velocity formulation is more significant compared to the length one, the former is origin-independent by design. This property makes it particularly suitable for calculations of HRS-OA invariants using approximated (variational or not) wave functions.