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PROOF COPY 020416JCP Dynamics and the breaking of a driven cage: I2 in solid Ar
 

Summary: PROOF COPY 020416JCP
PROOF
COPY
020416JCP
Dynamics and the breaking of a driven cage: I2 in solid Ar
Z. Bihary, R. Zadoyan, M. Karavitis, and V. A. Apkariana)
Department of Chemistry, University of California, Irvine, California 92697
Received 29 August 2003; accepted 4 February 2004
Pump­probe measurements of I2 in solid Ar are reported and analyzed to extract a description of
cage response to impulsive excitation, from the gentle kick, up to the breaking point. The most
informative data are obtained through wavepacket motion on cage-bound, but otherwise
dissociative, potentials where the chromophore acts as a transducer to drive the cage and to report
on the local dynamics. This general class of dynamics is identified and analyzed as a function of
energy in Ar, Kr, and Xe. The overdriven cage rebounds with a characteristic period of 1.2 ps that
shows little dependence on excitation amplitude, in all hosts. After rebound, the cage rings as a local
resonant mode in Ar, with a period of 1 ps and dephasing time of 3 ps. This mode remains at the
Debye edge in Kr and Xe, with periods of 630 and 800 fs, and dephasing times of 8 and 6 ps,
respectively. In the bound B-state, the cage fluctuates toward its dilated equilibrium structure on a
time scale of 3 ps, which is extracted from the down-chirp in the molecular vibrational frequency.
When kicked with excess energy of 4 eV, the Ar cage breaks with 50% probability, and the molecule

  

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

 

Collections: Chemistry