State-specific solvation for restricted active space spin-flip (RAS-SF) wave functions based on the polarizable continuum formalism

The restricted active space spin-flip (RAS-SF) formalism is a particular form of single-reference configuration interaction that can describe some forms of strong correlation at a relatively low cost and which has recently been formulated for the description of charge-transfer excited states. Here, we introduce both equilibrium and nonequilibrium versions of a state-specific solvation correction for vertical transition energies computed using RAS-SF wave functions, based on the framework of a polarizable continuum model (PCM). Ground-state polarization is described using the solvent's static dielectric constant and in the nonequilibrium solvation approach that polarization is modified upon vertical excitation using the solvent's optical dielectric constant. Benchmark calculations are reported for well-studied models of photo-induced charge transfer, including naphthalene dimer, C2H4 center dot center dot center dot C2F4, pentacene dimer, and perylene diimide (PDI) dimer, several of which are important in organic photovoltaic applications. For the PDI dimer, we demonstrate that the charge-transfer character of the excited states is enhanced in the presence of a low-dielectric medium (static dielectric constant epsilon(0) = 3) as compared to a gas-phase calculation (epsilon(0) = 1). This stabilizes mechanistic traps for singlet fission and helps to explain experimental singlet fission rates. We also examine the effects of nonequilibrium solvation on charge-separated states in an intramolecular singlet fission chromophore, where we demonstrate that the energetic ordering of the states changes as a function of solvent polarity. The RAS-SF + PCM methodology that is reported here provides a framework to study charge-separated states in solution and in photovoltaic materials. Published under an exclusive license by AIP Publishing.

Automated summary

The restricted active space spin-flip (RAS-SF) formalism is a cost-effective method for describing strong correlation in single-reference configuration interaction. In this study, we introduced both equilibrium and nonequilibrium solvation corrections for computing vertical transition energies using RAS-SF wave functions. Benchmark calculations were performed for various photo-induced charge transfer models, and the results demonstrate the importance of the RAS-SF + PCM methodology in studying charge-separated states in solution and photovoltaic materials.