New features: TD-PCM and local field effects
(new feature) Non-equilibrium Time-dependent Polarizable Continuum Model (TD-PCM) feature has been implemented in two flavors:
Inertial/dynamic splitting of the polarization charges. This approach stems from the assumption of a sudden excitation of the solute molecule. It considers the solvent polarization splitted in two parts: a part that is able to follow instantaneously the solute charge-density fluctuation (dynamic polarization charges), and another part that lag behind in the evolution with respect to the solute charge-density (inertial polarization charges).
Equation of motion for the polarization charges. This approach accounts for the history-dependent solvent polarization, ensuing from the frequency-dependent dielectric function describing the solvent. The implementation allows to use Debye or Drude-Lorentz dielectric models for the solvent.
- S. Corni, S. Pipolo, R. Cammi, J. Phys. Chem. A 2015, 119, 5405-5416. (Debye dielectric model)
- S. Pipolo, S. Corni, J. Phys. Chem. C 2016, 120, 28774-28781. (Drude-Lorentz dielectric model)
N.B. Previous implementation in Octopus assumed that the solvent was able to instantaneously equilibrate with the solute.
(new feature) Local field effects within PCM framework. The non-equilibrium polarization of the solvent due to possible electric fields applied have been included for static and time-dependent calculations.
Both new features allow us to couple the real-time evolution of the molecule electronic density with the non-equilibrium polarization response of the solvent in presence or absence of external electric fields. The new features apply only in the case of DFT and TDDFT.