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p-Benzoquinone in aqueous solution: Stark shifts in spectra, asymmetry in solvent structure

Öhrn, Anders LU and Aquilante, Francesco LU (2007) In Physical Chemistry Chemical Physics 9(4). p.470-480
Abstract
Results from a simulation of p-benzoquinone (PBQ) in water is presented. An explicit solvent representation is used together with a multiconfigurational ab initio quantum chemical method. The electronic n -> pi* transitions are studied in aqueous solution and the two such transitions are both blue-shifted but to different degree. Both non-equilibrium and many-body effects are found to have decisive influence on the solvation: despite stronger hydrogen bonding between solute and solvent in an excited state than in the ground state, there is a blue-shift, and the solvent structure around the non-polar PBQ is asymmetric, which is argued to come from special many-body effects. The unusual result of strengthened hydrogen bonds in the excited... (More)
Results from a simulation of p-benzoquinone (PBQ) in water is presented. An explicit solvent representation is used together with a multiconfigurational ab initio quantum chemical method. The electronic n -> pi* transitions are studied in aqueous solution and the two such transitions are both blue-shifted but to different degree. Both non-equilibrium and many-body effects are found to have decisive influence on the solvation: despite stronger hydrogen bonding between solute and solvent in an excited state than in the ground state, there is a blue-shift, and the solvent structure around the non-polar PBQ is asymmetric, which is argued to come from special many-body effects. The unusual result of strengthened hydrogen bonds in the excited state that follows from an excitation of a non-bonding electron on a proton acceptor, is explained by the near-linear Stark shift that is present in the transition. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Physical Chemistry Chemical Physics
volume
9
issue
4
pages
470 - 480
publisher
Royal Society of Chemistry
external identifiers
  • wos:000243564400006
  • scopus:33846240787
ISSN
1463-9084
DOI
10.1039/b613833k
language
English
LU publication?
yes
id
92dc5361-63f1-4a60-9e83-94b3346800ff (old id 676510)
date added to LUP
2007-12-14 13:44:06
date last changed
2017-09-17 06:59:59
@article{92dc5361-63f1-4a60-9e83-94b3346800ff,
  abstract     = {Results from a simulation of p-benzoquinone (PBQ) in water is presented. An explicit solvent representation is used together with a multiconfigurational ab initio quantum chemical method. The electronic n -> pi* transitions are studied in aqueous solution and the two such transitions are both blue-shifted but to different degree. Both non-equilibrium and many-body effects are found to have decisive influence on the solvation: despite stronger hydrogen bonding between solute and solvent in an excited state than in the ground state, there is a blue-shift, and the solvent structure around the non-polar PBQ is asymmetric, which is argued to come from special many-body effects. The unusual result of strengthened hydrogen bonds in the excited state that follows from an excitation of a non-bonding electron on a proton acceptor, is explained by the near-linear Stark shift that is present in the transition.},
  author       = {Öhrn, Anders and Aquilante, Francesco},
  issn         = {1463-9084},
  language     = {eng},
  number       = {4},
  pages        = {470--480},
  publisher    = {Royal Society of Chemistry},
  series       = {Physical Chemistry Chemical Physics},
  title        = {p-Benzoquinone in aqueous solution: Stark shifts in spectra, asymmetry in solvent structure},
  url          = {http://dx.doi.org/10.1039/b613833k},
  volume       = {9},
  year         = {2007},
}