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Resonant Raman, Hot, and Cold Luminescence of Iodine in Rare Gas Matrixes J. Almy, K. Kizer, R. Zadoyan, and V. A. Apkarian*
 

Summary: Resonant Raman, Hot, and Cold Luminescence of Iodine in Rare Gas Matrixes
J. Almy, K. Kizer, R. Zadoyan, and V. A. Apkarian*
Department of Chemistry, UniVersity of California, IrVine, California 92697-2025
ReceiVed: September 13, 1999; In Final Form: December 7, 1999
Spontaneous light emission (SLE) spectra induced by continuous wave excitation of iodine in rare gas matrixes
is analyzed from the perspective of semiclassical molecular dynamics. The three-time correlation functions
that describe the process are interpreted in terms of time circuits, where the reversibility of mechanics along
specified paths establishes the distinction between resonant Raman (RR) and fluorescence. The observed hot
luminescence (fluorescence from the vibrationally over-damped period of dynamics) is simulated, and the
underlying dynamics analyzed to describe vibrational dephasing, formation of stationary states, and
predissociation of I2(B) in matrixes. The extracted predissociation time of 3-5 ps in matrixes agrees with
time-domain measurements. The analysis allows the interpretation of liquid phase spectra which contain both
structured and unstructured SLE as strictly RR, suggesting that the unstructured component is due to linear
complexes. The spectra also contain vibrationally relaxed emissions from the cage-bound, doubly spin-orbit
excited I*I* states, which are prepared via sequential two-photon excitation with an intermediate state lifetime
of 2 ms, assigned to A(3
P1u). The two main emission bands, which shift by 300 cm-1
in proceeding from Ar
to Kr to Xe, are assigned to I*I*(1u) f I2(a(1g)), and I*I*(0g
+

  

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

 

Collections: Chemistry