Onset of decoherence:: Six-wave mixing measurements of vibrational decoherence on the excited electronic state of I2 in solid argon

Pump-probe, four-wave, and six-wave mixing measurements of I-2 isolated in solid argon are used to provide a clear experimental measure for the onset of vibrational quantum decoherence on the excited electronic state. The electronically resonant, six-wave mixing measurements bypass the rapid electronic dephasing, and measure the quantum cross-correlation between two packets launched on the B-state. The vibrational quantum coherence survives one period of motion, 400 fs, during which similar to2000 cm(-1) of energy is transferred to the lattice. The decoherence occurs during the second cycle of motion, while classically coherent motion measured via pump-probe spectroscopy using the same electronic resonances continues for similar to15 periods. This is contrasted with vibrational dephasing on the ground electronic surface, which lasts for 10(2) periods, as measured through time-resolved coherent anti-Stokes Raman scattering. The measurements and observables are discussed through time-circuit diagrams, and a mechanistic description of decoherence is derived through semiclassical analysis and simulations that reproduce the experiments. (C) 2004 American Institute of Physics.