An infrared study of the interaction-induced vibrational spectra of benzene in liquid binary mixtures containing CS2 and C6F6

Zoidis, Evangelos; Besnard, M.; Yarwood, J.

doi:10.1016/0301-0104(95)00126-9

Cited by 4 publications

(3 citation statements)

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“…In the last decade many nonlinear optical effects have been explored in studies of solvent and solvation dynamics, and it was shown that each technique projects onto certain types of molecular motion. For instance, while the optical Kerr effect probes solvent motions associated with anisotropic Raman polarizabilities, [8][9][10][11][12][13][14][15][16][17][18] farinfrared spectroscopy only senses dipolar molecular motions, [57][58][59] while optical absorption and emission spectroscopies cover all molecular motions that couple to the optical transition.…”

Section: Introductionmentioning

confidence: 99%

“…It is therefore not surprising that physical chemists have a vested interest in the exploration of liquid state dynamics. − Since molecular motions in liquids occur on time scales from tens of femtoseconds upward, it was not until ultrafast lasers became available that time-resolved studies of liquids and solutions became an important option. − In the last decade many nonlinear optical effects have been explored in studies of solvent and solvation dynamics, and it was shown that each technique projects onto certain types of molecular motion. For instance, while the optical Kerr effect probes solvent motions associated with anisotropic Raman polarizabilities, − far-infrared spectroscopy only senses dipolar molecular motions, − while optical absorption and emission spectroscopies cover all molecular motio...…”

Section: Introductionmentioning

confidence: 99%

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System−Bath Correlation Function Probed by Conventional and Time-Gated Stimulated Photon Echo

1996

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We show how in the framework of the multimode Brownian oscillator model the system-bath correlation function can be derived from conventional and time-gated stimulated photon echo experiments and consideration of the linear optical spectra. Experiments are performed on the infrared dye DTTCI in room temperature solutions of ethylene glycol, methanol, and acetonitrile. The obtained correlation function is the sum of several Brownian oscillators, of which four are attributed to intrachromophore vibrational dynamics and the other three to solute-solvent dynamics. The ultrafast part of the correlation function on the time scale of the excitation pulses is interpreted as a free induction decay-like effect due to impulsive excitation of spectrally broad underlying vibrational structure in the dye's electronic transition. The slower parts are assigned to multiple time scale solute-solvent dynamics. The effect of vibrational coherences on the echo measurements is also analyzed; this analysis permits the dissection of the correlation function into a part due to intrachromophore dynamics and a part due to solvation dynamics. The spectral densities associated with these latter oscillators are located in the far infrared, in the same spectral region as probed by the optical Kerr effect. The measurements, however, provide no definite answer to the question of whether these spectral densities are the same.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

System−Bath Correlation Function Probed by Conventional and Time-Gated Stimulated Photon Echo

1996

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“…Traditionally, the dynamics of atomic and molecular liquids are studied by far-infrared ͑FIR͒ absorption spectroscopy 3,4 or by Rayleigh-Raman scattering, [5][6][7][8] that measure the Fourier transform of the one-time correlation function of the dipole moment and polarizability, respectively. In the thermal range below 300 cm Ϫ1 , the fluctuations in these bulk properties are associated with the same lowfrequency intermolecular motions.…”

Section: Introductionmentioning

confidence: 99%

Time resolved four- and six-wave mixing in liquids. I. Theory

Steffen¹,

Fourkas

Duppen

1996

The Journal of Chemical Physics

155

154

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Low-frequency intermolecular dynamics in liquids is studied by ultrafast four-and six-wave mixing. The theory of these nonlinear optical processes is given for electronically nonresonant optical interactions up to fifth order in the electric field. The Born-Oppenheimer approximation is used to separate the motional part of the response functions from coordinate independent electronic hyperpolarizabilities. A large variety of experiments, involving far-infrared absorption, ordinary Rayleigh-Raman or hyper Rayleigh-Raman scattering is covered by this theory. The response in nonresonant six-wave mixing comprises four dynamically different processes. It is shown that one of the terms contains information on the time scale͑s͒ of intermolecular dynamics, that is not available from lower-order nonresonant experiments. For instance, homogenous and inhomogeneous contributions to line broadening can be distinguished. The optical response of harmonic nuclear motion is calculated for nonlinear coordinate dependence of the polarizabilities. Results for level-dependent and level-independent damping of the motion are compared. It is shown that level-dependent damping destroys the interference between different quantum mechanical pathways, yielding an extra contribution to the fifth-order response that has not been discussed before. When two or more nuclear modes determine the optical response, their relative contributions to the four-and six-wave mixing signals are in general different. These contributions are determined by the coordinate dependence of the electronic polarizability, which is usually not fully known. Model calculations are presented for the dynamic parameters of liquid CS 2. The theory of this paper will be employed in Part II, to analyze experimental results on femtosecond four-and six-wave mixing.

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