On the performance of quantum chemical methods to predict solvatochromic effects. The case of acrolein in aqueous solution
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On the performance of quantum chemical methods to predict solvatochromic effects. The case of acrolein in aqueous solution. / Aidas, Kestutis; Møgelhøj, Andreas; Nilsson, Elna Johanna Kristina; Johnson, Matthew Stanley; Mikkelsen, Kurt Valentin; Christiansen, Ove; Söderhjelm, Pär; Kongsted, Jacob.
I: Journal of Chemical Physics, Bind 128, 2008, s. 194503-1 to 194503-15.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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T1 - On the performance of quantum chemical methods to predict solvatochromic effects. The case of acrolein in aqueous solution
AU - Aidas, Kestutis
AU - Møgelhøj, Andreas
AU - Nilsson, Elna Johanna Kristina
AU - Johnson, Matthew Stanley
AU - Mikkelsen, Kurt Valentin
AU - Christiansen, Ove
AU - Söderhjelm, Pär
AU - Kongsted, Jacob
N1 - Paper id:: DOI: 10.1063/1.2918537
PY - 2008
Y1 - 2008
N2 - The performance of the Hartree–Fock method and the three density functionals B3LYP, PBE0, andCAM-B3LYP is compared to results based on the coupled cluster singles and doubles model inpredictions of the solvatochromic effects on the vertical n¿* and ¿* electronic excitationenergies of acrolein. All electronic structure methods employed the same solvent model, which isbased on the combined quantum mechanics/molecular mechanics approach together with adynamical averaging scheme. In addition to the predicted solvatochromic effects, we have alsoperformed spectroscopic UV measurements of acrolein in vapor phase and aqueous solution. Thegas-to-aqueous solution shift of the n¿* excitation energy is well reproduced by using all densityfunctional methods considered. However, the B3LYP and PBE0 functionals completely fail todescribe the ¿* electronic transition in solution, whereas the recent CAM-B3LYP functionalperforms well also in this case. The ¿* excitation energy of acrolein in water solution is foundto be very dependent on intermolecular induction and nonelectrostatic interactions. The computedexcitation energies of acrolein in vacuum and solution compare well to experimental data.
AB - The performance of the Hartree–Fock method and the three density functionals B3LYP, PBE0, andCAM-B3LYP is compared to results based on the coupled cluster singles and doubles model inpredictions of the solvatochromic effects on the vertical n¿* and ¿* electronic excitationenergies of acrolein. All electronic structure methods employed the same solvent model, which isbased on the combined quantum mechanics/molecular mechanics approach together with adynamical averaging scheme. In addition to the predicted solvatochromic effects, we have alsoperformed spectroscopic UV measurements of acrolein in vapor phase and aqueous solution. Thegas-to-aqueous solution shift of the n¿* excitation energy is well reproduced by using all densityfunctional methods considered. However, the B3LYP and PBE0 functionals completely fail todescribe the ¿* electronic transition in solution, whereas the recent CAM-B3LYP functionalperforms well also in this case. The ¿* excitation energy of acrolein in water solution is foundto be very dependent on intermolecular induction and nonelectrostatic interactions. The computedexcitation energies of acrolein in vacuum and solution compare well to experimental data.
M3 - Journal article
VL - 128
SP - 194503-1 to 194503-15
JO - The Journal of Chemical Physics
JF - The Journal of Chemical Physics
SN - 0021-9606
ER -
ID: 5979102