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Hybrid Monte Carlo simulations of vertical electronic transitions in acetone in aqueous solution

Öhrn, Anders LU and Karlström, Gunnar LU (2007) In Theoretical Chemistry Accounts 117(3). p.441-449
Abstract
A simulation of the n -> pi* absorption and the pi -> n 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... (More)
A simulation of the n -> pi* absorption and the pi -> n 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. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
excited state, Pauli repulsion, acetone, explicit solvent model
in
Theoretical Chemistry Accounts
volume
117
issue
3
pages
441 - 449
publisher
Springer
external identifiers
  • wos:000244691700010
  • scopus:33847702528
ISSN
1432-881X
DOI
10.1007/s00214-006-0172-7
language
English
LU publication?
yes
id
86e557fa-fc6d-4e5a-8bf9-ec702fe9ba39 (old id 670939)
date added to LUP
2007-12-19 10:12:45
date last changed
2017-06-18 04:21:55
@article{86e557fa-fc6d-4e5a-8bf9-ec702fe9ba39,
  abstract     = {A simulation of the n -> pi* absorption and the pi -> n 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.},
  author       = {Öhrn, Anders and Karlström, Gunnar},
  issn         = {1432-881X},
  keyword      = {excited state,Pauli repulsion,acetone,explicit solvent model},
  language     = {eng},
  number       = {3},
  pages        = {441--449},
  publisher    = {Springer},
  series       = {Theoretical Chemistry Accounts},
  title        = {Hybrid Monte Carlo simulations of vertical electronic transitions in acetone in aqueous solution},
  url          = {http://dx.doi.org/10.1007/s00214-006-0172-7},
  volume       = {117},
  year         = {2007},
}