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Physical Review Letters

Vibrational Multilevel Quantum Coherence due to Anharmonic Couplings in Intermolecular Hydrogen Bonds

Nils Huse, Karsten Heyne, J. Dreyer, Erik T. J. Nibbering, Thomas Elsaesser

Published Nov 4, 2003• 46 citations
Publisher

Abstract

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.

DOI
10.1103/physrevlett.91.197401

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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.
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We present the first infrared photon echo study of liquid water. For the O-H stretch vibration of HDO in D2O{\mathrm{D}}_{2}\mathrm{O}D2​O, femtosecond four-wave mixing experiments reveal an extraordinary short pure dephasing time T2∗{T}_{2}^{*}T2∗​ on the order of 90 fs. This unusually fast time scale of dephasing is rationalized by taking into account the large anharmonicity of the hydrogen bonded O-H stretching mode.
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.
The vibrational photon echo measurement employs short pulses of coherent infrared radiation to discriminate among line broadening processes of different time scales. The measurement has been analyzed with the optical Bloch equations, in which the coupling of a quantum three-level system to a bath is represented by dephasing times. A detailed treatment of vibrational dynamics in a molecular liquid requires a Hamiltonian model. As such models are more readily treated in classical than in quantum mechanics, we consider the calculation of the vibrational echo in classical mechanics. Vibrational echoes are calculated for a solvated anharmonic oscillator. The classical mechanical echo is shown to share attributes of a quantum mechanical calculation.