A perturbed-mean-field approach to the decay rates of excited vibrational states in extended systems: An application to I2(Ne)n

Adrian E. Roitberg, R. Benny Gerber, Mark A Ratner

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

A method for calculating decay rates of vibrational modes in large polyatomic systems is proposed and tested. The high frequency excited vibration is treated quantum mechanically, and the soft modes are described classically. The initial state is described by the hybrid quantum/ classical self-consistent-field (SCF) approximation. The formalism is based on a golden-rule expression. The driving potential is the difference between the full Hamiltonian and the mean field Hamiltonian (SCF) causing the decay of the initial state to final mixed quantum/classical SCF states. These states are calculated using an extension of the usual static mean-field techniques to systems with mixed quantum and classical degrees of freedom. The formalism for obtaining the mean-field states and calculating the decay rates is presented, and the method is applied to a diatomic molecule treated quantum mechanically, embedded in a 1D model for a rare gas cluster treated classically. The dependence of the eigenenergies of the quantum and the decay rates with temperature is studied. The influence on the system size is also presented and compared with the prediction of the isolated binary collision model. The effect of a change in the linear density of the cluster on the eigenenergies of the vibrational mode is presented.

Original languageEnglish
Pages (from-to)4355-4366
Number of pages12
JournalJournal of Chemical Physics
Volume100
Issue number6
Publication statusPublished - 1994

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Hamiltonians
vibrational states
decay rates
self consistent fields
Noble Gases
vibration mode
formalism
diatomic molecules
Molecules
rare gases
degrees of freedom
vibration
collisions
decay
predictions
approximation
Temperature
temperature

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

A perturbed-mean-field approach to the decay rates of excited vibrational states in extended systems : An application to I2(Ne)n. / Roitberg, Adrian E.; Benny Gerber, R.; Ratner, Mark A.

In: Journal of Chemical Physics, Vol. 100, No. 6, 1994, p. 4355-4366.

Research output: Contribution to journalArticle

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