Time resolved coherent anti-Stokes Raman scattering of I2 isolated in matrix argon: Vibrational dynamics on the ground electronic state

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Time-resolved, electronically resonant, coherent anti-Stokes Raman scattering is used to prepare and interrogate vibronic coherences of molecular iodine in matrix Ar. Coherences that involve evolution on the excited B(3Π0u) state, first- and third-order coherences, decay in less than one vibrational period (τ<300 fs). In contrast, as many as 200 vibrational periods of motion can be observed for Raman-prepared wave packets consisting of zero-phonon vibrational superpositions on the ground electronic state (second-order coherence). Packets consisting of v=4, 5 and v=3, 4, 5 on the X(1Σg) state decay with a half-life of 10±1 ps at 31 K, allowing a more accurate measure of vibrational level spacings and decoherence time than has been possible in frequency domain. The harmonic frequency of the molecule is reduced by 1.5 cm−1 (0.7%) in the matrix. The lack of recurrence in the excited electronic state ensures that the resonant anti-Stokes scattering arises only from the negative momentum component of the Raman packet. This momentum filter, which should be ubiquitous in condensed media, leads to a signal with deeper modulation than in the gas phase.