Solvation energies and electronic spectra in polar, polarizable media: Simulation tests of dielectric continuum theory

摘要: A dielectric continuum theory for the solvation of a polar molecule in polar, polarizable solvent is tested using computer simulations formaldehyde water. Many classes experiments, example those which measure solvent‐shifted vertical transition energies or electron transfer rates, require an explicit consideration electronic polarization. Due to computational cost simulating solvent, many simulation models employ non‐polarizable solute and molecules use relate properties system more realistic system. We have performed ground excited state both water, spectra we obtained are used test continuum, linear response predictions. Dielectric correctly predicts that free energy differences same The wrongly reorganization 30% smaller than solvent; simulations, differ by only 6%. suggest fails because it assumes states exist size cavity whereas radius increases 20% after transition. account change adding non‐linear solute–solvent coupling theory, find resulting predictions just outside error bounds from simulation. corrections undesired incorrect side‐effect predicting fluctuations far seen simulations. This reveals inherent difficulty devising simple, fully self‐consistent solvation.