Analytical Hartree–Fock calculation of the dynamical polarizabilities α, β, and γ of molecules in solution

Abstract

We present a theory for the calculation of the self-consistent-field dynamical polarizability and hyperpolarizabilities of molecular solutes described within the framework of the polarization continuum model. The formulation is characterized by the use of a cavity accurately modeled on the molecular shape of the solvated compound, and of a frequency dependent dielectric permittivity for the solvent. Calculations of the components of polarizability ␣, first and second hyperpolarizabilities ␤ and ␥ tensors of H 2 CO in water and in benzene are reported and discussed.

Polarizabilities in the condensed phase and the local fields problem: A direct reaction field formulation

“…It seems that experimentalists and theoreticians very often rely on this ''molecule in cavity'' model in order to account for bulk effects on measured polarizabilities [3][4][5][6] where the Lorentz field 7 is taken as a local field. Also, computational efforts to describe solvent effects on ͑hyper͒polarizabilities are dominated by the continuum approach, [8][9][10][11] invariably reporting larger ͑hyper͒polarizabili-ties in solution than in the gas phase. Recently we repeated 12 the PCM ͑Ref.…”

Equation of motion for the solvent polarization apparent charges in the polarizable continuum model: Application to time-dependent CI

“…The latter is treated as continuum described by a complex dielectric permittivity (ω). Within PCM,the effective time-dependent electronic Hamiltonian for the solute may be written as: 4,6 H =Ĥ 0 + q(Ψ; t) ·V +V (t)…”

“…In fact, when the molecule is in solution (or in even more complex environment), the electronic dynamics is coupled to the behavior of the solvent, that is in general delayed resulting in a far-from trivial dynamics of the overall solute+solvent system. Within the Polarizable Continuum Model (PCM) 3 for solvation the general theoretical framework to investigate such dynamics was set long ago, [4][5][6] but only in a recent paper, 7 we have shown a convenient way to take into account such coupled dynamics in real time. This approach was based on the definition of equations of motion (EOM) 8 for the time-dependent apparent charges that in PCM generate the time-dependent reaction field.…”

Novel organic material with potential NLO application - electronic and spectroscopic properties

“…In the case of HF calculations the scaling factor of 0.8929 was used. The solvent effect on the absorption bands were studied by TD [27] DFT level of theory with a combination of polarized continuum model (PCM) [28][29][30]. Novel organic material with potential NLO application -electronic and spectroscopic properties…”