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Effect of pressure on molecular photodissociation in matrices: Molecular dynamics simulations of Cl, in Xe
 

Summary: Effect of pressure on molecular photodissociation in matrices:
Molecular dynamics simulations of Cl, in Xe
R. Alimi
Department of Physical Chemistry and the Fritz Haber Center for Molecular Dynamics,
The Hebrew Uniuersity of Jerusalem, Jerusalem 91904, Israel
V. A. Apkarian and R. B. Gerbera)
Department of Chemistry, University of California, Irvine, CaIifornia 92717
(Received 17 December 1991; accepted 15 September 1992)
A theoretical study is presented on the photodissociation dynamics of Cl2 in crystalline xenon
at 100 K, and within a range of pressure between 0 and 100 kbar. Temperature/pressure en-
semble molecular dynamics simulations were carried out. The potentials used were accurate
enough to reproduce the experimental equation of state of solid xenon. .The results show that
the photodissociation quantum yield varies strongly with pressure, falling from 30% at zero
pressure, to 2% at 12.5 kbar, and 0% at higher pressures. These yields are in good agree-
ment with experimental measurements. This behavior is found to be due to, the strong effect
of pressure on the librational (rotational) amplitudes of the Cl, molecule and to the sharp
dependence of the photodissociation yield on the molecular orientation in the reagent cage.
I. INTRODUCTION
The photodissociation of diatomic molecules in rare-
gas crystals provides an attractive and fundamental model

  

Source: Apkarian, V. Ara - Department of Chemistry, University of California, Irvine

 

Collections: Chemistry