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ELSEVIER Chemical Physics 189 ( 1994) 26 l-272 Adiabatic approximation and non-adiabatic effects
 

Summary: Chemical
Physics
ELSEVIER Chemical Physics 189 ( 1994) 26 l-272
Adiabatic approximation and non-adiabatic effects
for open-shell atoms in an inert solvent:
F atoms in solid Kr
A.I. Krylov a,b,R.B. Gerber a,b,V.A. Apkarian b
aDepartment ofPhysicalChemistry and The Fritz Haber Research Centerfor Molecular Dynamics, The Hebrew University,
Jerusalem 91904, Isruel
b Department of Chemistry, Universiq of California, Irvine, CA 92717, USA
Received 17 June 1994
Abstract
The dynamics of P-state F atoms in solid Kr is studied by molecular dynamics simulations in two frameworks: (i) The
adiabatic approximation, in which nuclear motion is confined to the lowest adiabatic potential surface of the system; (ii) A
method that treats semiclassically non-adiabatic transitions between electronic states in the course of the dynamics. The
simulations deal with the spectroscopy of the F atom at different lattice sites, and with orbital reorientation dynamics due to the
coupling with lattice vibrations. Also explored is migration of the F atom, following the preparation of an exciplex Kr: F -
which dissociates radiatively in the lattice. Some of the main findings are: (1) p-orbital reorientation dynamics on very short
timescales (t < 20 fs) is dominated by non-adiabatic mechanisms. Adiabatically, reorientation effects have timescales of the
order of 0.25 ps or longer. (2) Lattice vibrations of particular symmetry types are particularly efficient in inducing p-orbital

  

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

 

Collections: Chemistry