Temperature dependence of light scattering from neat benzene with femtosecond pulses: are we seeing molecules librate?

Snijders

Duppen

2000

Articles you may be interested inFifth-order two-dimensional Raman spectroscopy of liquid water, crystalline ice Ih and amorphous ices: Sensitivity to anharmonic dynamics and local hydrogen bond network structure Interaction induced effects in the nonlinear Raman response of liquid CS 2 : A finite field nonequilibrium molecular dynamics approach A finite field molecular dynamics ͑MD͒ method has been developed to calculate the off-resonant Raman response of liquids. The method has been used to calculate the third-and fifth-order optical responses of CS 2 . From the third-order response, the intensity of third-order cascading processes has been estimated. The calculated ratio between the fifth-order intensity and the intensity of the third-order cascading processes supports experimental observations, claiming that two-dimensional Raman spectra are dominated by third-order cascading processes.

Section: Theorymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The third- and fifth-order nonlinear Raman response of liquid CS2 calculated using a finite field nonequilibrium molecular dynamics method

Snijders

Duppen

2000

“…Third-order time domain Raman experiments such as the ͑heterodyned͒ optical Kerr effect 1,2 and transient grating scattering 3,4 make it possible to observe the motion of atoms and molecules in liquids in real time. Since the response is determined by the time evolution of the first-order susceptibility, all motions that affect this susceptibility are observable.…”

Section: Introductionmentioning

confidence: 99%

Collision effects in the nonlinear Raman response of liquid carbon disulfide

Swart

Jensen

et al. 2002

Electronic polarization effect on low-frequency infrared and Raman spectra of aprotic solvent: Molecular dynamics simulation study with charge response kernel by second order Møller-Plesset perturbation method A model of the polarizability of carbon disulfide dimers was constructed, using polarizabilities from accurate time-dependent density functional theory calculations as reference. This direct reaction field model takes dipole-induced dipole effects, induced multipole effects and effects due to the overlap of the electronic clouds into account in an approximate way. The importance of the induced multipole and the overlap effects is investigated. This polarizability model is subsequently used to calculate the third-order time-domain Raman response of liquid carbon disulfide. These results are compared to experimental data and earlier calculated response in which only dipole-induced dipole effects on the polarizability were included. The multipole effects are found to give a significant contribution to the subpico second part of the third-order Raman response.

“…4 -15 Examples of these techniques are the ͑heterodyned͒ optical Kerr effect 4,5 and transient grating scattering. 6,7 These experiments probe the evolution of the first-order susceptibility ͑the macroscopic polarizability͒ after impulsive excitation of the system, allowing observation of the liquid motion in real time. The time-domain data of these third-order nonlinear optical experiments are related to the frequency-domain spectra from spontaneous light scattering by Fourier transformation.…”

Section: Introductionmentioning

confidence: 99%

Liquid xenon as an ideal probe for many-body effects in impulsive Raman scattering

Boeijenga

Pugžlys

et al. 2002

The molecular origins of the two-dimensional Raman spectrum of an atomic liquid. I. Molecular dynamics simulationThe collision induced effects in the third-order Raman response of liquid xenon have been studied both experimentally and theoretically. The effect of electron cloud overlap on the polarizability of xenon dimers was studied using accurate time-dependent density functional theory calculations. The dimer polarizabilities were used to fit parameters in a direct reaction field model that can be generalized to condensed phase systems. This model was employed in molecular dynamics simulations in order to calculate the impulsive Raman response of liquid xenon. Excellent agreement is found between the shape of the calculated and the measured anisotropic part of the response. The shape of this response is little affected by the electron overlap effects, but the intensity is strongly influenced by it. The shape of the isotropic response is predicted to be strongly dependent on electron overlap effects.