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The I*(2P1/2)-I*(2P1/2) Contact Pair Emission in Condensed Media: A Molecular Spring-Gauge for Cavity Sizing
 

Summary: The I*(2P1/2)-I*(2P1/2) Contact Pair Emission in Condensed Media: A Molecular
Spring-Gauge for Cavity Sizing
M. Karavitis and V. A. Apkarian*
Department of Chemistry, UC IrVine, California 92697
ReceiVed: April 25, 2002; In Final Form: June 6, 2002
The I*I*(0g
+) f I*I(B(0u
+)) emission spectra obtained in neat Ar, Kr, Xe, and in mixed Kr/Xe matrixes is
reported. The emission from the strictly cage-bound initial state shifts linearly with Kr/Xe mixing fraction,
without significant change in spectral width. The line shapes in mixed-hosts are understood in terms of the
statistics of sites in the solid solutions. The pure-host line shapes are reproduced through Monte Carlo
simulations using accurately known I-Rg potentials. The analysis yields a refined I*I* potential and provides
a calibration curve to readout the cavity size of isolation from the observed emission peak shift.
Introduction
The interaction between spin-excited iodine atoms, I*(2P1/2)
+ I*(2P1/2), leads to three potentials, 0g
+, 0g
-, and 1u, all three
of which are repulsive (see Figure 1).2 At contact, the spin-flip
transitions to I*(2P1/2) + I(2P3/2) and I(2P1/2) + I(2P1/2) are dipole-

  

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

 

Collections: Chemistry