On the performance of quantum chemical methods to predict solvatochromic effects: The case of acrolein in aqueous solution.
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/1153805
- author
- Aidas, Kestutis ; Mo̸gelho̸j, Andreas ; Nilsson, Elna J K LU ; Johnson, Matthew S ; Mikkelsen, Kurt V ; Christiansen, Ove ; Söderhjelm, Pär LU and Kongsted, Jacob LU
- organization
- publishing date
- 2008
- 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 (AIP)
- external identifiers
-
- wos:000256205200031
- pmid:18500876
- scopus:44349143797
- pmid:18500876
- ISSN
- 0021-9606
- DOI
- 10.1063/1.2918537
- 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
- ff55f7a3-9bab-49fd-9983-73d264bc007d (old id 1153805)
- date added to LUP
- 2016-04-01 12:09:39
- date last changed
- 2023-04-05 01:29:34
@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 (AIP)}}, 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}}, doi = {{10.1063/1.2918537}}, volume = {{128}}, year = {{2008}}, }