Most probable path in phase space for a radiationless transition in a molecule

Alexey V. Sergeev, Bilha Segev

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

We study a radiationless transition in a polyatomic molecule when the electronic energy of an excited electronic state is transferred to the vibrational degrees of freedom of the nuclei, and when some nuclear coordinates change abruptly. This jump between the donor energy surface and the acceptor one gives the initial conditions for the subsequent dynamics on the acceptor surface, and the partition of energy between competing accepting modes. In the Wigner representation, the physical problem of recognizing the accepting modes for a radiationless vibronic relaxation reduces to the mathematical problem of finding the maximum of a function of many variables under a constraint. The function is the initial Wigner function of the nuclei and the constraint is energy conservation. In a harmonic approximation for the potential surfaces, the problem is equivalent to finding the distance from a given point to a multidimensional ellipsoid. This geometrical problem is solved in closed form. For nonharmonic potentials, the optimization problem is solved perturbatively.

Original languageEnglish
Pages (from-to)1769-1789
Number of pages21
JournalJournal of Physics A: Mathematical and General
Volume35
Issue number7
DOIs
Publication statusPublished - 22 Feb 2002
Externally publishedYes

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Probable
Phase Space
Molecules
Path
Nucleus
molecules
nuclei
polyatomic molecules
energy conservation
Surface potential
Electronic states
Electronics
ellipsoids
electronics
Interfacial energy
Surface Potential
surface energy
Wigner Function
partitions
Surface Energy

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Statistical and Nonlinear Physics
  • Mathematical Physics

Cite this

Most probable path in phase space for a radiationless transition in a molecule. / Sergeev, Alexey V.; Segev, Bilha.

In: Journal of Physics A: Mathematical and General, Vol. 35, No. 7, 22.02.2002, p. 1769-1789.

Research output: Contribution to journalArticle

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