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On the performance of quantum chemical methods to predict solvatochromic effects: The case of acrolein in aqueous solution.

Aidas, Kestutis; Mo̸gelho̸j, Andreas; Nilsson, Elna J K; Johnson, Matthew S; Mikkelsen, Kurt V; Christiansen, Ove; Söderhjelm, Pär LU and Kongsted, Jacob LU (2008) In Journal of Chemical Physics 128(19). p.1-194503
Abstract
The performance of the Hartree-Fock method and the three density functionals B3LYP, PBE0, and CAM-B3LYP is compared to results based on the coupled cluster singles and doubles model in predictions of the solvatochromic effects on the vertical n-->pi(*) and pi-->pi(*) electronic excitation energies of acrolein. All electronic structure methods employed the same solvent model, which is based on the combined quantum mechanics/molecular mechanics approach together with a dynamical averaging scheme. In addition to the predicted solvatochromic effects, we have also performed spectroscopic UV measurements of acrolein in vapor phase and aqueous solution. The gas-to-aqueous solution shift of the n-->pi(*) excitation energy is well... (More)
The performance of the Hartree-Fock method and the three density functionals B3LYP, PBE0, and CAM-B3LYP is compared to results based on the coupled cluster singles and doubles model in predictions of the solvatochromic effects on the vertical n-->pi(*) and pi-->pi(*) electronic excitation energies of acrolein. All electronic structure methods employed the same solvent model, which is based on the combined quantum mechanics/molecular mechanics approach together with a dynamical averaging scheme. In addition to the predicted solvatochromic effects, we have also performed spectroscopic UV measurements of acrolein in vapor phase and aqueous solution. The gas-to-aqueous solution shift of the n-->pi(*) excitation energy is well reproduced by using all density functional methods considered. However, the B3LYP and PBE0 functionals completely fail to describe the pi-->pi(*) electronic transition in solution, whereas the recent CAM-B3LYP functional performs well also in this case. The pi-->pi(*) excitation energy of acrolein in water solution is found to be very dependent on intermolecular induction and nonelectrostatic interactions. The computed excitation energies of acrolein in vacuum and solution compare well to experimental data. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Physics
volume
128
issue
19
pages
1 - 194503
publisher
American Institute of Physics
external identifiers
  • wos:000256205200031
  • pmid:18500876
  • scopus:44349143797
ISSN
0021-9606
DOI
10.1063/1.2918537
language
English
LU publication?
yes
id
ff55f7a3-9bab-49fd-9983-73d264bc007d (old id 1153805)
date added to LUP
2008-10-08 12:31:59
date last changed
2017-08-27 04:07:09
@article{ff55f7a3-9bab-49fd-9983-73d264bc007d,
  abstract     = {The performance of the Hartree-Fock method and the three density functionals B3LYP, PBE0, and CAM-B3LYP is compared to results based on the coupled cluster singles and doubles model in predictions of the solvatochromic effects on the vertical n-->pi(*) and pi-->pi(*) electronic excitation energies of acrolein. All electronic structure methods employed the same solvent model, which is based on the combined quantum mechanics/molecular mechanics approach together with a dynamical averaging scheme. In addition to the predicted solvatochromic effects, we have also performed spectroscopic UV measurements of acrolein in vapor phase and aqueous solution. The gas-to-aqueous solution shift of the n-->pi(*) excitation energy is well reproduced by using all density functional methods considered. However, the B3LYP and PBE0 functionals completely fail to describe the pi-->pi(*) electronic transition in solution, whereas the recent CAM-B3LYP functional performs well also in this case. The pi-->pi(*) excitation energy of acrolein in water solution is found to be very dependent on intermolecular induction and nonelectrostatic interactions. The computed excitation energies of acrolein in vacuum and solution compare well to experimental data.},
  author       = {Aidas, Kestutis and Mo̸gelho̸j, Andreas and Nilsson, Elna J K and Johnson, Matthew S and Mikkelsen, Kurt V and Christiansen, Ove and Söderhjelm, Pär and Kongsted, Jacob},
  issn         = {0021-9606},
  language     = {eng},
  number       = {19},
  pages        = {1--194503},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {On the performance of quantum chemical methods to predict solvatochromic effects: The case of acrolein in aqueous solution.},
  url          = {http://dx.doi.org/10.1063/1.2918537},
  volume       = {128},
  year         = {2008},
}