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Solvent effects on excitation energies using state-specific TD-DFT method with polarizable continuum model based on constrained equilibrium thermodynamics

Abstract

Nonequilibrium solvation effect needs to be treated properly in study of electronic absorption processes of solute since the solvent polarization is in non-equilibrium with the excited-state charge density of the solute. In this work, we developed a state specific(SS) method based on the novel nonequilibrium solvation model with constrained equilibrium manipulation to account for solvation effects in electronic absorption process. Time-dependent density functional theory(TD-DFT) is adopted to calculate electronic excitation energies and a polarizable continuum model is employed in treatment of bulk solvent effects on both the ground and excited electronic states. The equations based on this novel nonequilibrium solvation model in the framework of TDDFT to calculate vertical excitation energy are presented and implemented in the Q-Chem package. The implementation is validated by comparing reorganization energies for charge transfer excitations between two atoms obtained from Q-Chem and those of a two-sphere model. Solvent effects on electronic transitions of coumarin 153(C153), acetone, pyridine, (2E)-3-(3,4-dimethoxyphenyl)-1-(2-hydroxyphenyl) prop-2-en-1-one (DMHP), and uracil in different solvents are investigated using the newly developed code. Our results show that the obtained vertical excitation energies as well as spectral shifts generally agree better with available experimental values than those using the traditional nonequlibrium solvation model. This new model is thus appropriate to study nonequilibrium excitation processes in solution.

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Publication details

The article was received on 19 Aug 2017, accepted on 08 Nov 2017 and first published on 10 Nov 2017


Article type: Paper
DOI: 10.1039/C7CP05673G
Citation: Phys. Chem. Chem. Phys., 2017, Accepted Manuscript
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    Solvent effects on excitation energies using state-specific TD-DFT method with polarizable continuum model based on constrained equilibrium thermodynamics

    T. Bi, L. Xu, F. Wang, M. Ming and X. Li, Phys. Chem. Chem. Phys., 2017, Accepted Manuscript , DOI: 10.1039/C7CP05673G

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