Dissociation dynamics of vibrationally excited van der Waals clusters: I2XY→I2+X+Y (X, Y=He, Ne)

George C Schatz, Victoria Buch, Mark A Ratner, Robert B. Gerber

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Abstract

The dynamics of sequential dissociation processes of the type XI 2(v)Y→X+I2(v′)Y→X+Y+I2(v″ )(X, Y=Ne, He) are studied using classical trajectory calculations and a recently presented classical version of the time-dependent self-consistent field (TDSCF) method. The results obtained indicate the presence of significant dynamical correlation effects of the rare-gas atoms on each other despite the negligible direct interaction between them; this is in qualitative agreement with experimental findings. Good agreement is found for the rate constants and the variation with rare gas as well as the branching ratios (NeI 2He→NeI2+He vs→I2He+Ne) calculated from TDSCF and from classical trajectories. Both classical trajectories and TDSCF show an essentially impulsive dissociation mechanism, in which dissociation typically follows a considerable number of vibrations, and is due to a relatively rare internal hard collision between an I atom and the rare gas. As in the three-body I2X case, this mechanism differs from that in the RRKM strong coupling model. Energy- and momentum-gap relations, based on the weak-coupling picture, are found to be relatively successful but fail to describe the dynamics quantitatively.

Original languageEnglish
Pages (from-to)1808-1822
Number of pages15
JournalJournal of Chemical Physics
Volume79
Issue number4
Publication statusPublished - 1983

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Noble Gases
self consistent fields
rare gases
Trajectories
trajectories
dissociation
Atoms
atoms
Rate constants
Momentum
momentum
vibration
collisions
interactions
energy

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Dissociation dynamics of vibrationally excited van der Waals clusters : I2XY→I2+X+Y (X, Y=He, Ne). / Schatz, George C; Buch, Victoria; Ratner, Mark A; Gerber, Robert B.

In: Journal of Chemical Physics, Vol. 79, No. 4, 1983, p. 1808-1822.

Research output: Contribution to journalArticle

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