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Chemical Physics Letters

Multilevel vibrational dephasing and vibrational anharmonicity from infrared photon echo beats

Andrei Tokmakoff, Alfred S. Kwok, Randall S. Urdahl, R. S. Francis, M. D. Fayer

Published Mar 1, 1995• 63 citations

Abstract

Vibrational photon echo experiments were performed on the asymmetric CO stretching mode of tungsten hexacarbonyl in glassy dibutylphthalate as a function of temperature using sub-picosecond infrared pulses (1976 cm−1) from a free electron laser. The echo decays display pronounced beats and are bi-exponential. The beats and bi-exponential decays arise because the bandwith of the pulses exceed the vibrational anharmonicity, leading to the excitation and dephasing of a multilevel coherence. From the beat frequency, the anharmonicity is determined to be 14.7 cm−1. From the bi-exponential decay components, the temperature-dependent vibrational dephasing of both the v = 0 → 1 and v = 1 → 2 transitions are determined.

DOI: 10.1016/0009-2614(95)00068-f

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An account is given of the first infrared vibrational photon echo experiments conducted in liquids and a glasses. The experiments were performed on the CO stretching mode of the solute tungsten hexacarbonyl (W(CO)6) at approximately 5.05 micrometers (approximately 1980 cm-1) in the solvents 2-methytetrahydrofuran, and 2-methylpentane (2-MP). In 2-MP, it was possible to observe the photon echo decay at room temperature and follow the temperature dependence from room temperature to 10 K. The photon echo experiments were conducted using the Stanford superconducting-linear-accelerator-pumped Free Electron Laser as the source of tunable ps infrared pulses.

The first infrared vibrational photon echo experiments conducted in a liquid and a glass are reported. The experiments were performed on the CO stretching mode of tungsten hexacarbonyl at 5.1 \ensuremath{\mu}m (1960 ${\mathrm{cm}}^{\mathrm{\ensuremath{-}}1}$) in 2-methyltetrahydrofuran over the temperature range 300 to 16 K using picosecond pulses from the free electron laser at Stanford University. In addition, the first vibrational population relaxation measurements spanning a temperature range that takes a system from a liquid to a supercooled liquid to a glass are reported.

The first infrared vibrational photon echo experiments conducted in a liquid and a glass are reported. The experiments were performed on the CO stretching mode of tungsten hexacarbonyl at 5.1 micrometers (1960 cm-1) in 2-methyltetrahydrofuran over the temperature range 300 K to 16 K using picosecond pulses from the free electron laser at Stanford University. In addition, the first vibrational population relaxation measurements spanning a temperature range that takes a system from a liquid to a supercooled liquid to a glass are reported.

The influence of the environment on vibrational dynamics, and especially on the vibrational dephasing time, is investigated for a simple system : DCl in a van der Waals solid (N2 lattice). Photon echo experiments are performed using the infrared free electron laser CLIO. In solid nitrogen, decay times of the third order polarization are in the picosecond range. In the case of the isolated DCl monomers in van der Waals interaction with the host, the observed signals are interpreted in term of a rapid spectral diffusion. The two different stretching modes of DCl dimers, perturbed in a different way by the weak hydrogen bond, exhibit different coherence times, reflecting the influence of the interaction strength between the molecules.

Femtosecond three-pulse photon-echo studies of acetic acid dimers in solution reveal multilevel coherence of O-H stretching excitations caused by the anharmonic coupling between the high-frequency stretching and low-frequency hydrogen-bond motions. We demonstrate for the first time that such multilevel coherence determines the nonexponential decay of the macroscopic O-H stretching polarization, whereas spectral diffusion processes play a minor role. The dephasing time of individual vibrational transitions contributing to the overall polarization is approximately 200 fs.