Details
| Original language | English |
|---|---|
| Pages (from-to) | 69-73 |
| Number of pages | 5 |
| Journal | Chemical Physics |
| Volume | 402 |
| Early online date | 10 Apr 2012 |
| Publication status | Published - 19 Jun 2012 |
Abstract
The photodissociation of diphenylmethyl chloride (DPMCl) can lead to the formation of radicals or ions depending on the environment. We use first-principles molecular dynamics simulations to study the photochemistry of DPMCl in the gas phase and in aqueous solution. In the gas phase simulations the photoexcitation leads to the formation of a radical pair. For the photoreaction of DPMCl in a polar solution a two-step process is observed: the actual photoreaction proceeds diabatically and leads to the formation of a radical pair. This radical pair is subsequently transformed into an ion pair via an electron transfer reaction. The ultrafast process explains the experimentally observed formation of ions on a sub-picosecond timescale.
Keywords
- Carbocations, Density-functional calculations, First-principles molecular dynamics, Photochemical reaction, Reaction mechanism
ASJC Scopus subject areas
- Physics and Astronomy(all)
- General Physics and Astronomy
- Chemistry(all)
- Physical and Theoretical Chemistry
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In: Chemical Physics, Vol. 402, 19.06.2012, p. 69-73.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - First-principles simulation of a photoinduced carbocation formation
AU - Coughtrie, D. J.
AU - Frank, Irmgard
AU - Friedrichs, Jana
N1 - Funding Information: We thank Herbert Mayr and Regina de Vivie-Riedle for bringing the subject to our attention and for valuable discussions. This work was supported by the Deutsche Forschungsgemeinschaft : SFB 749 ‘Dynamik und Intermediate molekularer Transformationen’ and project FR 1246/3–1. Part of the calculations were performed at the HLRN supercomputing system (project nic00017).
PY - 2012/6/19
Y1 - 2012/6/19
N2 - The photodissociation of diphenylmethyl chloride (DPMCl) can lead to the formation of radicals or ions depending on the environment. We use first-principles molecular dynamics simulations to study the photochemistry of DPMCl in the gas phase and in aqueous solution. In the gas phase simulations the photoexcitation leads to the formation of a radical pair. For the photoreaction of DPMCl in a polar solution a two-step process is observed: the actual photoreaction proceeds diabatically and leads to the formation of a radical pair. This radical pair is subsequently transformed into an ion pair via an electron transfer reaction. The ultrafast process explains the experimentally observed formation of ions on a sub-picosecond timescale.
AB - The photodissociation of diphenylmethyl chloride (DPMCl) can lead to the formation of radicals or ions depending on the environment. We use first-principles molecular dynamics simulations to study the photochemistry of DPMCl in the gas phase and in aqueous solution. In the gas phase simulations the photoexcitation leads to the formation of a radical pair. For the photoreaction of DPMCl in a polar solution a two-step process is observed: the actual photoreaction proceeds diabatically and leads to the formation of a radical pair. This radical pair is subsequently transformed into an ion pair via an electron transfer reaction. The ultrafast process explains the experimentally observed formation of ions on a sub-picosecond timescale.
KW - Carbocations
KW - Density-functional calculations
KW - First-principles molecular dynamics
KW - Photochemical reaction
KW - Reaction mechanism
UR - http://www.scopus.com/inward/record.url?scp=84861880054&partnerID=8YFLogxK
U2 - 10.1016/j.chemphys.2012.04.003
DO - 10.1016/j.chemphys.2012.04.003
M3 - Article
AN - SCOPUS:84861880054
VL - 402
SP - 69
EP - 73
JO - Chemical Physics
JF - Chemical Physics
SN - 0301-0104
ER -