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

研究成果: Article査読

11 被引用数 (Scopus)

抄録

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.

本文言語English
ページ(範囲)1397-1404
ページ数8
ジャーナルChemPhysChem
14
7
DOI
出版ステータスPublished - 2013 5 10

ASJC Scopus subject areas

  • 原子分子物理学および光学
  • 物理化学および理論化学

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