Jump to main content
Jump to site search

Issue 18, 2012
Previous Article Next Article

H-abstraction is more efficient than cistrans isomerization in (4-methylcyclohexylidene) fluoromethane. An ab initio molecular dynamics study

Author affiliations

Abstract

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[double bond, length as m-dash]C double bond, 4MCF is expected to undergo cistrans 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 ππ* state. This state is strongly mixed with πσ* 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 sp2 carbons and CHF dissociation. In contrast, the amount of trajectories undergoing torsion around the double bond, and therefore cistrans isomerization, is marginal. The H-abstraction reaction is ultrafast, taking place in less than 60 fs.

Graphical abstract: H-abstraction is more efficient than cis–trans isomerization in (4-methylcyclohexylidene) fluoromethane. An ab initio molecular dynamics study

Back to tab navigation

Publication details

The article was received on 17 Aug 2011, accepted on 28 Sep 2011 and first published on 18 Oct 2011


Article type: Paper
DOI: 10.1039/C1CP22646K
Citation: Phys. Chem. Chem. Phys., 2012,14, 6241-6249
  •   Request permissions

    H-abstraction is more efficient than cistrans isomerization in (4-methylcyclohexylidene) fluoromethane. An ab initio molecular dynamics study

    D. Kinzel, J. González-Vázquez and L. González, Phys. Chem. Chem. Phys., 2012, 14, 6241
    DOI: 10.1039/C1CP22646K

Search articles by author

Spotlight

Advertisements