p-Benzoquinone in aqueous solution: Stark shifts in spectra, asymmetry in solvent structure
(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:
https://lup.lub.lu.se/record/676510
- author
- Öhrn, Anders LU and Aquilante, Francesco LU
- organization
- publishing date
- 2007
- 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
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
- id
- 92dc5361-63f1-4a60-9e83-94b3346800ff (old id 676510)
- date added to LUP
- 2016-04-01 15:22:53
- date last changed
- 2023-04-07 09:56:57
@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}},
doi = {{10.1039/b613833k}},
volume = {{9}},
year = {{2007}},
}