To accelerate reactive events in molecular dynamics simulations we introduce a general bias potential scheme which depends only on the electronic degrees of freedom of the reactive system. This electronic reaction coordinate, which is expressed in terms of a penalty function of the one-electron orbital energies, has been applied to study different reaction pathways of s-cis-butadiene. Three different reactive channels have been identified: the cis/trans isomerization, the s-cis/s-trans isomerization, and the symmetry allowed cyclization. For the latter, despite the fact that the Woodward-Hoffmann rules are guided by the butadiene frontier orbitals, biasing only these orbitals is not enough to drive the system toward cyclization, but a low-lying valence shell orbital needs to be included.

Scanning Reactive Pathways with Orbital Biased Molecular Dynamics

GUIDONI, Leonardo;
2005-01-01

Abstract

To accelerate reactive events in molecular dynamics simulations we introduce a general bias potential scheme which depends only on the electronic degrees of freedom of the reactive system. This electronic reaction coordinate, which is expressed in terms of a penalty function of the one-electron orbital energies, has been applied to study different reaction pathways of s-cis-butadiene. Three different reactive channels have been identified: the cis/trans isomerization, the s-cis/s-trans isomerization, and the symmetry allowed cyclization. For the latter, despite the fact that the Woodward-Hoffmann rules are guided by the butadiene frontier orbitals, biasing only these orbitals is not enough to drive the system toward cyclization, but a low-lying valence shell orbital needs to be included.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11697/21598
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