Hybrid Monte Carlo simulations of vertical electronic transitions in acetone in aqueous solution |
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Authors: | Anders Öhrn Gunnar Karlström |
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Institution: | (1) Department of Theoretical Chemistry, Chemical Centre, Lund University, P.O. Box 124, 221 00 Lund, Sweden |
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Abstract: | A simulation of the absorption and the fluorescence of acetone in aqueous solution is reported. The model has an explicit solvent representation with an effective
ab initio treatment of the solute. The model attempts to balance quantum chemistry, intermolecular interactions and statistical thermodynamics.
It includes a non-electrostatic perturbation on the solute which models the solute–solvent exchange repulsion and the restriction
put on the electronic structure of the solute by the antisymmetry to the solvent. The solvent shift to the absorption transition
is found to be between 0.16 and 0.21 eV; the shift to the fluorescence transition is found to be between 0.02 and 0.05 eV.
The simulation supports the conclusion that the first peak in the fluorescence spectrum of acetone is from a single molecule
in equilibrium with the solvent, not from an excimer. |
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Keywords: | Acetone Explicit solvent model Pauli repulsion Excited state |
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