Separation of temperature and density effects on collision-induced Rayleigh and Raman line shapes of liquid carbon disulfide

Hegemann, B.; Jonáš, J.

doi:10.1063/1.448286

Cited by 53 publications

(10 citation statements)

References 62 publications

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“…The low-frequency components were attributed to reorientation, and the high-frequency components were assigned to gaslike translations. 24 Even though it is now known that reorientation dominates the entire DLS spectrum of carbon disulfide, 26−28 these pioneering studies nevertheless showed that density and temperature can in fact be separable in the low-frequency Raman spectrum of molecular liquids. Ladanyi et al used molecular dynamics (MD) and Monte Carlo simulations to evaluate the temperature and density dependences of the spectral moments of low-frequency Raman spectra of argon and xenon.…”

Section: Introductionmentioning

confidence: 99%

Toward in Situ Measurement of the Density of Liquid Benzene Using Optical Kerr Effect Spectroscopy

Bender¹,

Cohen²,

He³

et al. 2016

J. Phys. Chem. B

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The high-frequency portion of the optical Kerr effect (OKE) spectrum of benzene shifts to higher frequency with decreasing temperature at constant pressure. This behavior has been interpreted previously in terms of an increase in librational frequencies due to the decrease in free volume with liquid densification. However, decreasing temperature also provides less access to the more repulsive portion of the intermolecular potential, which would cause the blue edge of the spectrum to red-shift. To explore the relative importance of these phenomena, molecular dynamics simulations of benzene are used to isolate the effects of temperature and density on the spectrum. The simulations show that, at constant density, the high-frequency portion of the spectrum shifts to lower frequency with decreasing temperature. In contrast, at constant temperature, the high-frequency portion of the spectrum shifts to higher frequency with increasing density. These results indicate that density plays a greater role in determining the position of the blue edge of the low-frequency Raman spectrum of benzene than does temperature. Empirical fits show that the effects of changing density or temperature are similar in experimental and simulated OKE spectra. Furthermore, line-shape analysis of simulated spectra under isochoric and isothermal conditions shows that the effects of density and temperature are separable, suggesting that OKE spectroscopy is a viable technique for in situ measurement of the density of van der Waals liquids.

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Section: Introductionmentioning

confidence: 99%

Toward in Situ Measurement of the Density of Liquid Benzene Using Optical Kerr Effect Spectroscopy

Bender¹,

Cohen²,

He³

et al. 2016

J. Phys. Chem. B

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“…By these spectroscopic techniques in time and frequency domains, intermolecular dynamics of a simple molecular liquid such as CS 2 , 5,6,11,25 halogenated methanes, 11,32,39 benzene 6,11,39 and its derivatives, 18,21 and more complicated hydrogen-bonded molecular liquid such as water, [22][23][24] alcohol, 16 ethylene glycol 19 and their solutions 8,9,20 has been studied. General agreement exists in the intermolecular dynamics in terms of relaxation modes and oscillation modes that are closely related to the microscopic environment in which the molecules are located.…”

Section: Introductionmentioning

confidence: 99%

Molecular dynamics of thiophene homologues investigated by femtosecond optical Kerr effect and low frequency Raman scattering spectroscopies

Kamada¹,

Ueda²,

Ohta³

et al. 1998

The Journal of Chemical Physics

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We present the results of femtosecond optical heterodyn detected optical Kerr effect (OHD-OKE) spectroscopy and low frequency Raman scattering spectroscopy for three thiophene homologues (C4H4X, X=O, S, and Se). The observed OHD-OKE transients were analyzed both in time and frequency domains. Fourier transformed OHD-OKE data were directly compared with the corresponding spontaneous Raman scattering spectra. The reorientation lifetimes for furan (O), thiophene (S) and selenophene (Se) were determined to be 0.9, 2.0 and 3.2 ps, respectively, and were fairly explained in terms of the Stokes-Einstein-Debye relation. Their subpicosecond dynamics was analyzed with an antisymmetric Gaussian function and a skewed function developed by Bucaro and Litoviz, which gave good curve fits to observed data. Librational and translational dynamics of the molecules was discussed in terms of microscopic environments formed by neighboring molecules and the results of intermolecular interaction energy calculations by an ab initio molecular orbital method.

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“…First, we will present the experimental observations using Raman spectroscopy on the ν 1 -2ν 2 CO 2 Fermi dyad domain, followed by those on the induced (ν 2 and ν 3 ) and allowed (ν 1 and 2ν 2 ) modes of CS 2 . Then, we will rationalize these observations using the collision induced framework of Madden et al for the forbidden CS 2 modes, 18,20,21,[23][24][25][26][27][28][29][30][31][32]35 and vibrational relaxation models to discuss the departures from ideality probed by the allowed CO 2 and CS 2 modes. Finally, we will discuss the non ideality of the mixture from the existence of two distinct solvation regimes with a transition characterised by a plateau domain found in the evolution of the spectroscopic observables with the concentration.…”

Section: Fig 1 Pressure-composition Diagram Of the Binary Mixtures mentioning

confidence: 99%

“…[4][5][6][7][8][9][10][11][12][13][14][15][16][17] In dense phase, the aim was to provide insight on the nature and time scale of the intermolecular interactions from "allowed" vibrational spectra or from the analysis of collision induced (CI) spectra which are unique probes of the multi-body interactions. [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] The study of the interaction of carbon dioxide with molecular liquids and complex fluids as ionic liquids is a field of current interest, motivated not only from the fundamental point of view but mainly under the impetuous motivation of understanding the interactions of CO 2 in the field of environmental studies. [67][68][69][70] Surprisingly, in this context, studies of the CO 2 -CS 2 binary mixture are extremely scarce.…”

Section: Introductionmentioning

confidence: 99%

Assessing the non-ideality of the CO2-CS2 system at molecular level: A Raman scattering study

Besnard

Cabaço²,

Coutinho

et al. 2013

The Journal of Chemical Physics

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The dense phase of CO 2 -CS 2 mixtures has been analysed by Raman spectroscopy as a function of the CO 2 concentration (0.02-0.95 mole fractions) by varying the pressure (0.5 MPa up to 7.7 MPa) at constant temperature (313 K). The polarised and depolarised spectra of the induced (ν 2 , ν 3 ) modes of CS 2 and of the ν 1 -2ν 2 Fermi resonance dyad of both CO 2 and CS 2 have been measured. Upon dilution with CO 2 , the evolution of the spectroscopic observables of all these modes displays a "plateau-like" region in the CO 2 mole fraction 0.3-0.7 never previously observed in CO 2 -organic liquids mixtures. The bandshape and intensity of the induced modes of CS 2 are similar to those of pure CS 2 up to equimolar concentration, after which variations occur. The preservation of the local ordering from pure CS 2 to equimolar concentration together with the non-linear evolution of the spectroscopic observables allows inferring that two solvation regimes exist with a transition occurring in the plateau domain. In the first regime, corresponding to CS 2 concentrated mixtures, the liquid phase is segregated with dominant CS 2 clusters, whereas, in the second one, CO 2 monomers and dimers and CO 2 -CS 2 hetero-dimers coexist dynamically on a picosecond time-scale. It is demonstrated that the subtle interplay between attractive and repulsive interactions which provides a molecular interpretation of the non-ideality of the CO 2 -CS 2 mixture allows rationalizing the volume expansion and the existence of the plateau-like region observed in the pressure-composition diagram previously ascribed to the proximity of an upper critical solution temperature at lower temperatures.

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Separation of temperature and density effects on collision-induced Rayleigh and Raman line shapes of liquid carbon disulfide

Cited by 53 publications

References 62 publications

Toward in Situ Measurement of the Density of Liquid Benzene Using Optical Kerr Effect Spectroscopy

Toward in Situ Measurement of the Density of Liquid Benzene Using Optical Kerr Effect Spectroscopy

Molecular dynamics of thiophene homologues investigated by femtosecond optical Kerr effect and low frequency Raman scattering spectroscopies

Assessing the non-ideality of the CO2-CS2 system at molecular level: A Raman scattering study

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