Monte Carlo simulations of absorption and fluorescence spectra in ellipsoidal nanocavities

The absorption and fluorescence spectra of a model solute molecule dissolved in a CH3I solvent confined in nanoscale ellipsoidal cavities have been simulated for solutions with densities equal to 1.4, 2.0, and 2.2 g/cm(3). The model solute is a diatomic molecule with an electronic charge-transfer transition. Monte Carlo simulations have been performed for solutions confined in hydrophobic prolate and oblate ellipsoidal cavities of varying size. The results of the absorption and fluorescence spectra are compared with previous simulations of confined solvents in spherical cavities. The solute and solvent molecule probability density distributions have been calculated and are used to interpret the spectra. An umbrella sampling approach is used to obtain accurate results for the solute probability distributions.