A joint time-dependent density-functional theory for excited states of electronic systems in solution

Abstract

We present a novel joint time-dependent density-functional theory for the description of solute-solvent systems in time-dependent external potentials. Starting with the exact quantum-mechanical action functional for both electrons and nuclei, we systematically eliminate solvent degrees of freedom and thus arrive at coarse-grained action functionals which retain the highly accurate \emph{ab initio} description for the solute and are, in principle, exact. This procedure allows us to examine approximations underlying popular embedding theories for excited states. Finally, we introduce a novel approximate action functional for the solute-water system and compute the solvato-chromic shift of the lowest singlet excited state of formaldehyde in aqueous solution, which is in good agreement with experimental findings.

11 pages

References in corpus (4)

• Joint density-functional theory for electronic structure of solvated systems
• Dynamical density functional theory for dense atomic liquids
• Classical density-functional theory of inhomogeneous water including explicit molecular structure and nonlinear dielectric response
• "Kohn-Shamification" of the classical density-functional theory of inhomogeneous polar molecular liquids with application to liquid hydrogen chloride