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- W2020486511 abstract "Third-order nonlinear IR spectroscopy has been used to study the vibrational population relaxation and the vibrational dephasing dynamics of the CN stretching mode of Fe(CN)64- in D2O. Transient-grating signals in the magic-angle condition show a biexponential decay upon the excitation of the T1u mode of the CN stretching motion. A fast-decaying component (∼700 fs) of the transient-grating signal is attributed to the rapid equilibration between the T1u mode and the Raman-active modes. The time scale of the slow-decaying component is around 23 ps, which corresponds to the vibrational population relaxation from the v = 1 state of the CN stretching mode. Anisotropy of the transient-grating signal decays with a time constant of 2.6 ps, which is due to the time evolution of the superposition states of the triply degenerate T1u modes. Three-pulse photon-echo measurements showed that the correlation function of the frequency fluctuations decays biexponentially with time constants of 80 fs and 1.5 ps. The time scales of the decay of the correlation function are similar to those for SCN- in D2O even though the coupling strength of the solute−solvent interaction depends on the systems. On the basis of these results, we discuss the vibrational dynamics of the CN stretching mode of Fe(CN)64- in D2O." @default.
- W2020486511 created "2016-06-24" @default.
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- W2020486511 date "2004-02-01" @default.
- W2020486511 modified "2023-09-24" @default.
- W2020486511 title "Vibrational Population Relaxation and Dephasing Dynamics of Fe(CN)<sub>6</sub><sup>4-</sup> in D<sub>2</sub>O with Third-Order Nonlinear Infrared Spectroscopy" @default.
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- W2020486511 doi "https://doi.org/10.1021/jp0369847" @default.
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