One-particle density matrix polarization susceptibility tensors.

The electric field-induced change in the one-electron density has been expressed as a series of the one-particle density matrix susceptibilities interacting with the spatial distribution of the electric field. The analytic approximate expressions are derived at the Hartree-Fock theory, which serves as a basis for the construction of the generalized model that is designed for an arbitrary form of wavefunction and any type of one-particle density matrix. It is shown that it is possible to accurately predict the changes in the one-electron ground-state density of water molecule in a spatially uniform electric field, as well as in spatially non-uniform electric field distribution generated by point charges. When both linear and quadratic terms with respect to the electric field are accounted for, the electric field-induced polarization energies, dipole moments, and quadrupole moments are quantitatively described by the present theory in electric fields ranging from weak to very strong (0.001-0.07 a.u.). It is believed that the proposed model could open new routes in quantum chemistry for fast and efficient calculations of molecular properties in condensed phases.