Nuclear flux densities during a model pericyclic reaction with energies well above and below the potential barrier

Timm Bredtmann, Hirohiko Kono, Jörn Manz, Kosuke Nakamura, Christian Stemmle

Research output: Contribution to journalArticlepeer-review

11 Citations (Scopus)

Abstract

Pericyclic reactions with energies E well above the potential energy barrier B (case E>B) proceed with quantum nuclear flux densities (j) which are essentially proportional to the nuclear densities ρ in the femtosecond time domain. This corresponds to the definition of classical (cl) mechanics, jcl=clρcl, with almost constant velocity vcl. For the other case E<B, however, that is, in the domain of coherent tunneling, we discover the opposite trend, that is, (j) has maximum value close to the barrier where ρ is a minimum (in fact where ρ is close to zero). The general conclusion is that quantum mechanical nuclear flux densities may be at variance from traditional expectations based on classical trajectories. This prediction calls for experimental demonstration. The counter-intuitive proof-of-principle is demonstrated for a simple, one-dimensional model of the Cope rearrangement of semibullvalene.

Original languageEnglish
Pages (from-to)1397-1404
Number of pages8
JournalChemPhysChem
Volume14
Issue number7
DOIs
Publication statusPublished - 2013 May 10

Keywords

  • molecular dynamics
  • nuclear flux densities
  • pericyclic reactions
  • quantum reaction dynamics
  • tunneling

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry

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