Details
| Original language | English |
|---|---|
| Pages (from-to) | 10825-10829 |
| Number of pages | 5 |
| Journal | Chemistry - A European Journal |
| Volume | 15 |
| Issue number | 41 |
| Early online date | 13 Oct 2009 |
| Publication status | Published - 19 Oct 2009 |
Abstract
The photochemistry of diphenyloxirane has been investigated by using static density functional theory and first-principles molecular dynamics. We optimised potential-energy surfaces for both the disrotatory and the conrotatory pathway in the first excited state. Although the disrotatory pathway does not seem to be favoured en ergetically, we get only the disrotatory product during the molecular dynamics simulations. This can be attributed to the "on-the-fly" description of the electronic structure in a first-principles molecular dynamics simulation. The different photochemical behaviour of aryl oxiranes and unsubstituted oxirane is due to different shapes of the frontier orbitais.
Keywords
- Density functional calculations, Molecular dynamics, Photochemistry, Reaction mechanisms, Ring-opening reactions
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
- Organic Chemistry
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In: Chemistry - A European Journal, Vol. 15, No. 41, 19.10.2009, p. 10825-10829.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Mechanism of electrocyclic ring-opening of diphenyloxirane
T2 - 40 Years after Woodward and Hoffmann
AU - Friedrichs, Jana
AU - Frank, Irmgard
PY - 2009/10/19
Y1 - 2009/10/19
N2 - The photochemistry of diphenyloxirane has been investigated by using static density functional theory and first-principles molecular dynamics. We optimised potential-energy surfaces for both the disrotatory and the conrotatory pathway in the first excited state. Although the disrotatory pathway does not seem to be favoured en ergetically, we get only the disrotatory product during the molecular dynamics simulations. This can be attributed to the "on-the-fly" description of the electronic structure in a first-principles molecular dynamics simulation. The different photochemical behaviour of aryl oxiranes and unsubstituted oxirane is due to different shapes of the frontier orbitais.
AB - The photochemistry of diphenyloxirane has been investigated by using static density functional theory and first-principles molecular dynamics. We optimised potential-energy surfaces for both the disrotatory and the conrotatory pathway in the first excited state. Although the disrotatory pathway does not seem to be favoured en ergetically, we get only the disrotatory product during the molecular dynamics simulations. This can be attributed to the "on-the-fly" description of the electronic structure in a first-principles molecular dynamics simulation. The different photochemical behaviour of aryl oxiranes and unsubstituted oxirane is due to different shapes of the frontier orbitais.
KW - Density functional calculations
KW - Molecular dynamics
KW - Photochemistry
KW - Reaction mechanisms
KW - Ring-opening reactions
UR - http://www.scopus.com/inward/record.url?scp=70350223590&partnerID=8YFLogxK
U2 - 10.1002/chem.200901152
DO - 10.1002/chem.200901152
M3 - Article
AN - SCOPUS:70350223590
VL - 15
SP - 10825
EP - 10829
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 41
ER -