Vibrational Lifetimes and Spectral Shifts in Supercritical Fluids as a Function of Density:  Experiments and Theory

Myers, D. J.; Shigeiwa, Motoyuki; Fayer, M. D.; Cherayil, Binny J.

doi:10.1021/jp992717i

Cited by 59 publications

(62 citation statements)

References 75 publications

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“…Thus, the isolated molecule is an important reference point. Compari-son of the IVR rate in supercritical fluid solvents to the gas phase rate by Fayer and co-workers, [9][10][11][12] who examine W͑CO) 6 , and by von Benten et al, 13 who study benzene, reveals the extent of the solvent influence in these systems. In addition to the supercritical fluid experiments, Yoo et al [15][16][17] directly compare IVR in both the room temperature gas and in liquid solutions for various acetylenic molecules.…”

Section: Introductionmentioning

confidence: 98%

“…1 Although many studies examine vibrational relaxation in either the gas phase 2-5 or in solution, [6][7][8] only a few experiments directly compare the relaxation dynamics for the isolated and solvated molecule using the same technique. [9][10][11][12][13][14][15][16][17] In this paper we examine the influence that solvation has on IVR and IET by comparing the vibrational relaxation of CH 3 I in various solvents and in the isolated molecule.…”

Section: Introductionmentioning

confidence: 99%

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Vibrational relaxation of CH3I in the gas phase and in solution

Elles

Cox

Crim

2004

The Journal of Chemical Physics

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Transient electronic absorption measurements reveal the vibrational relaxation dynamics of CH 3 I following excitation of the C-H stretch overtone in the gas phase and in liquid solutions. The isolated molecule relaxes through two stages of intramolecular vibrational relaxation ͑IVR͒, a fast component that occurs in a few picoseconds and a slow component that takes place in about 400 ps. In contrast, a single 5-7 ps component of IVR precedes intermolecular energy transfer ͑IET͒ to the solvent, which dissipates energy from the molecule in 50 ps, 44 ps, and 16 ps for 1 M solutions of CH 3 I in CCl 4 , CDCl 3 , and (CD 3 ) 2 CO, respectively. The vibrational state structure suggests a model for the relaxation dynamics in which a fast component of IVR populates the states that are most strongly coupled to the initially excited C-H stretch overtone, regardless of the environment, and the remaining, weakly coupled states result in a secondary relaxation only in the absence of IET.

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Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Vibrational relaxation of CH3I in the gas phase and in solution

Elles

Cox

Crim

2004

The Journal of Chemical Physics

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“…For example, in Appendix E, the force correlation function is decomposed into density correlation functions, and the resulting expression has been used by Banchi, Cherayil, Fayer, and their co-workers for calculating vibrational relaxation rate. 47,48 We now apply the Gaussian factorization scheme to calculate the third-order Raman response function. To begin, the polarizability tensor is written in Fourier space as…”

Section: B Direct Gaussian Factorizationmentioning

confidence: 99%

“…Dynamic decomposition schemes have been widely used in the theoretical studies of solvation dynamics, energy relaxation and dephasing, charge transfer, etc. [45][46][47][48] One such scheme invokes the Gaussian factorization of density fluctuations at different times. The equilibrium distribution broken by the factorization approximation is partly reconstructed by incorporating the liquid distribution function.…”

Section: Introductionmentioning

confidence: 99%

Calculations of nonlinear spectra of liquid Xe. I. Third-order Raman response

Cao

Yang

2002

The Journal of Chemical Physics

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The one-particle Green's function method in the Dirac-Hartree-Fock framework. I. Second-order valence ionization energies of Ne through XeThe microscopic interactions and dynamics probed by third-order Raman spectroscopy in an atomic liquid ͑Xe͒ are explored within the Drude oscillator model, both numerically and analytically. Many-body polarization effects reduce the coefficient of the effective dipole-induced-dipole tensor. The isotropic part of the effective dipole-induced-dipole tensor arises primarily from the three-body interaction and is short-ranged. With an isotropic sample, the Raman response in any polarization geometry can be rigorously decomposed into an isotropic component and an anisotropic component, which primarily measure the strength and evolution of the two-body and three-body interactions, respectively. An interesting result from our analysis is the derivation of the standard mode-coupling equation for the intermediate scattering function and the mode-coupling equation for the bilinear density mode using Gaussian factorization of the memory kernel and the mean spherical approximation of the direct correlation function. The initial moment expansion along with the Gaussian factorization scheme allows us to predict the temporal profile of the Raman response function with reasonable accuracy. Furthermore, the Kirkwood superposition scheme approximates the Raman correlation function with pair distribution functions and time correlation functions and allows us to predict the ratio of the pair, three-particle, and four-particle contributions. These results, though obtained for Xe, are generally helpful in interpreting third-order spectroscopies of other liquids.

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confidence: 99%

Vibrational Energy Relaxation Dynamics of XH Stretching Vibrations of Aromatic Molecules in the Electronic Excited State

Ebata

2010

Hydrogen Bonding and Transfer in the Excited State

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The vibrational energy relaxation (VER) of polyatomic molecules has been the central issue in many of the chemical reactions in condensed phase [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] as well as in gas phase . The vibrational energy introduced to the molecule is immediately redistributed within the molecule or to the surrounding molecules. Among many vibrations investigated, the VER of the OH and NH stretching vibrations may be most important from the viewpoint of understanding the dynamics of the H-bonding of protic solvent molecules as well as biologically relevant molecules [42][43][44][45][46][47][48]. VER of the electronically excited OH stretching vibration of aromatic molecules and their hydrogen-bonded cluster is especially interesting. Most of the aromatic molecules having an OH group become more acidic upon electronic excitation, leading to hydrogen/proton transfer reactions [49][50][51][52][53][54][55][56][57][58][59][60][61][62]. We expect that vibrational excitation may lead to additional effects.In this review, we report the study of the intramolecular and intracluster vibrational energy redistribution (IMVR and ICVR), vibrational predissociation (VP) and isomerization of molecules and their clusters in the S 1 state by using UV-IR double-resonance (DR) spectroscopy (Figure 2.1) [63][64][65][66][67]. In this spectroscopy, the molecule or the cluster in a supersonic jet is excited to the zero-point level of S 1 by UV laser light, and is further excited to the XH stretch vibrational level by a tunable IR laser light. VER of vibrationally excited molecules and clusters is observed by dispersed fluorescence spectroscopy. After the UV-IR DR excitation to the XH stretch level, the molecule or the cluster emits a broad fluorescence in a wide energy region owing to fast IMVR or ICVR. If the internal energy is high enough to break the cluster, it dissociates by VP and emission of the fragment is observed. We can distinguish these processes by measuring the dispersed

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Vibrational Lifetimes and Spectral Shifts in Supercritical Fluids as a Function of Density: Experiments and Theory

Cited by 59 publications

References 75 publications

Vibrational relaxation of CH3I in the gas phase and in solution

Vibrational relaxation of CH3I in the gas phase and in solution

Calculations of nonlinear spectra of liquid Xe. I. Third-order Raman response

Vibrational Energy Relaxation Dynamics of XH Stretching Vibrations of Aromatic Molecules in the Electronic Excited State

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