Modeling Molecular Systems at Extreme Pressure by an Extension of the Polarizable Continuum Model (PCM) Based on the Symmetry-Adapted Cluster-Configuration Interaction (SAC-CI) Method: Confined Electronic Excited States of Furan as a Test Case.

Abstract

Novel molecular photochemistry can be developed by combining high pressure and laser irradiation. For studying such high-pressure effects on the confined electronic ground and excited states, we extend the PCM (polarizable continuum model) SAC (symmetry-adapted cluster) and SAC-CI (SAC-configuration interaction) methods to the PCM-XP (extreme pressure) framework. By using the PCM-XP SAC/SAC-CI method, molecular systems in various electronic states can be confined by polarizable media in a smooth and flexible way. The PCM-XP SAC/SAC-CI method is applied to a furan (C4H4O) molecule in cyclohexane at high pressure (1-60 GPa). The relationship between the calculated free-energy and cavity volume can be approximately represented with the Murnaghan equation of state. The excitation energies of furan in cyclohexane show blueshifts with increasing pressure, and the extents of the blueshifts significantly depend on the character of the excitations. Particularly large confinement effects are found in the Rydberg states. The energy ordering of the lowest Rydberg and valence states alters under high-pressure. The pressure effects on the electronic structure may be classified into two contributions: a confinement of the molecular orbital and a suppression of the mixing between the valence and Rydberg configurations. The valence or Rydberg character in an excited state is, therefore, enhanced under high pressure.