Interaction-induced Raman and IR spectra of liquid CS<sub>2</sub>

Dayan, E.; Dervil, E.; Loisel, J.; Pinan-Lucarré, Jean-Paul; Tarjus, Gilles

doi:10.1080/00268979200102221

Cited by 6 publications

(2 citation statements)

References 23 publications

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“…[79][80][81] The intensity evolution can be nicely fitted using a third order polynomial and clearly departs from a straight line drawn to guide the eyes between the two extreme concentrations, FIG. 9.…”

Section: Carbon Disulfidementioning

confidence: 99%

“…18,21,[23][24][25][26][27][28][29] This analysis is based on physical considerations due to the lack of detailed theoretical treatment on CI spectra of binary mixtures, 81 which, even available, has limited application because many molecular properties would be required and most of them are unknown. 28 In this theoretical framework, the Raman activity of the ν 2 and ν 3 modes is mainly due to a dipole-induced quadrupole interaction (A -α) mechanism (see discussion in the supplementary material 117 ).…”

Section: A Analysis Of the Induced Modes Of Csmentioning

confidence: 99%

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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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Section: Carbon Disulfidementioning

confidence: 99%