Vibrational coherence of I2 in solid Kr

Time-resolved coherent anti-Stokes Raman scattering, with a resolution of 20 fs, is used to prepare a broadband vibrational superposition on the ground electronic state of I-2 isolated in solid Kr. The coherent evolution of a packet consisting of nu=1-6 is monitored for as many as 1000 periods, allowing a precise analysis of the material response and radiation coherence. The molecular vibrations are characterized by omega(e)=211.330(2) cm(-1), omega(e)x(e)=0.6523(6) cm(-1), omega(e)y(e)=2.9(1)x10(-3) cm(-1); the dephasing rates at 32 K range from 110 ps for nu=1 to 34 ps for nu=6, with nu dependence: gamma(nu)=8.5x10(-3)+4.9x10(-4)nu(2)+2.1x10(-6)nu(4) ps(-1). The signal amplitude is also modulated at omega(q)=41.56(3) cm(-1); which can be interpreted as coupling between the molecule and a local mode. The surprising implication is that this resonant local mode is decoupled from the lattice phonons, a finding that cannot be rationalized based on a normal-mode analysis. (C) 2004 American Institute of Physics.