Frequency-dependent current density tensors as density functions of dynamic polarizabilities

Abstract

Relationships accounting for contributions to the first-order charge density ρ(1) and current density J(1), induced in the electrons of a molecule by a monochromatic plane wave, have been obtained via time-dependent quantum mechanical perturbation theory. Their gauge invariance and invariance in passive translations of the coordinate system have been demonstrated (i) within the (long wavelengths) electric dipole approximation, in which only the electric field contributions to these densities are required, and (ii) within the electric quadrupole approximation, in which nonseparable terms provided by the magnetic field and by the electric field gradient, assumed uniform over the molecular domain, are needed. It is shown that the physical meaning of current density tensors depending on the frequency ω of the monochromatic wave shone on the molecule, and corresponding to derivatives of the current density J(1)(r, ω) with respect to components of the perturbing fields, is that of property density. Therefore, frequency-dependent current density tensors can be interpreted as the integrand function in 3d-space integrals defining dynamic molecular response tensors, e.g., electric dipole, mixed electric dipole-magnetic dipole, and electric dipole-quadrupole polarizabilites. Plots of current density tensors are expected to provide important information on the molecular domains giving dominant contributions to these properties.