Coupling molecular density functional theory with converged selected configuration interaction methods to study excited states in aqueous solution

Abstract

This paper presents the first implementation of a coupling between advanced wavefunction theories and molecular density functional theory (MDFT). This method enables the modeling of solvent effect into quantum mechanical (QM) calculations by incorporating an electrostatic potential generated by solvent charges into the electronic Hamiltonian. Solvent charges are deduced from the spatially and angularly dependent solvent particle density. Such a density is obtained through the minimization of the functional associated with the molecular mechanics (MM) Hamiltonian describing the interaction between the fluid particles. The introduced QM/MDFT framework belongs to QM/MM family of methods, but its originality lies in the use of MDFT as the MM solver, offering two main advantages. First, its functional formulation makes it competitive with respect to sampling-based molecular mechanics. Second, it preserves a molecular-level description lost in macroscopic continuum approaches. The excited state properties of water and formaldehyde molecules solvated into water have been computed at the selected configuration interaction (SCI) level. The excitation energies and dipole moments have been compared with experimental data and previous theoretical work. A key finding is that using the Hartree–Fock method to describe the solute allows for predicting the solvent charge around the ground state with sufficient precision for the subsequent SCI calculations of excited states. This significantly reduces the computational cost of the described procedure, paving the way for the study of more complex molecules.