Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 14, Issue 18, Pages 6241-6249Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c1cp22646k
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Funding
- Deutsche Forschungsgemeinschaft, Israel [GO-1059/7-3]
- Deutsche Forschungsgemeinschaft, Palestine [GO-1059/7-3]
- Deutsche Forschungsgemeinschaft, Germany [GO-1059/7-3]
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Non-adiabatic molecular dynamics simulations have been performed in the fluoro-olefin (4-methylcyclohexylidene) fluoromethane (4MCF) using multiconfigurational CASSCF (complete active space self-consistent field) on-the-fly calculations. As an olefin containing a C=C double bond, 4MCF is expected to undergo cis-trans isomerization after light irradiation. However, ab initio molecular dynamics shows that a preferential dissociation of atomic hydrogen is taking place after population transfer to the bright pi pi* state. This state is strongly mixed with pi sigma* states allowing dissociation in the electronic excited state before deactivation to the ground state occurs. A minor amount of trajectories experiences F-dissociation, followed by pyramidalization at the sp(2) carbons and CHF dissociation. In contrast, the amount of trajectories undergoing torsion around the double bond, and therefore cis-trans isomerization, is marginal. The H-abstraction reaction is ultrafast, taking place in less than 60 fs.
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