Interaction-induced spectra of CO<sub>2</sub>

Madden, Paul A.; Cox, T. I.

doi:10.1080/00268978500102281

Cited by 21 publications

(4 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…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%

“…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%

“…[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%

See 2 more Smart Citations

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

View full text Add to dashboard Cite

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.

show abstract

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

confidence: 99%

Section: A Analysis Of the Induced Modes Of Csmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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

View full text Add to dashboard Cite

show abstract

“…Numerous spectroscopic studies devoted to the dynamic properties of CS2 have been reported in the literature. The main aim of these studies was to explore the origin and time scale of the molecular scale phenomena from vibrational spectral lines as well as from symmetry-forbidden (SF) interaction induced spectra (IIS), which are unique probes of multi molecular interactions 7,[45][46][47][48][49][50][51][52] . On the other hand, the pressure effects upon the dynamics of the liquid have been investigated in the past two decades mainly using far-infrared (FIR) absorption and low frequency Raman scattering techniques.…”

Section: Introductionmentioning

confidence: 99%

Structure and dynamics of liquid CS2: Going from ambient to elevated pressure conditions

Skarmoutsos

Mossa

Samios

2016

The Journal of Chemical Physics

View full text Add to dashboard Cite

Molecular dynamics simulation studies were performed to investigate the structural and dynamic properties of liquid carbon disulfide (CS) from ambient to elevated pressure conditions. The results obtained have revealed structural changes at high pressures, which are related to the more dense packing of the molecules inside the first solvation shell. The calculated neutron and X-ray structure factors have been compared with available experimental diffraction data, also revealing the pressure effects on the short-range structure of the liquid. The pressure effects on the translational, reorientational, and residence dynamics are very strong, revealing a significant slowing down when going from ambient pressure to 1.2 GPa. The translational dynamics of the linear CS molecules have been found to be more anisotropic at elevated pressures, where cage effects and librational motions are reflected on the shape of the calculated time correlation functions and their corresponding spectral densities.

show abstract

The femtosecond birefringence of CO2: from the high pressure gas to the liquid phase

Zhou

Constantine

Harrel

et al. 2000

J. Raman Spectrosc.

View full text Add to dashboard Cite

The optical heterodyne detected (OHD) birefringence of CO2 gas in the reduced density range from ρ/ρc = 0.09–0.82 and in the room temperature liquid are reported. Each birefringent response is separated into an electronic, rotational diffusion and non‐diffusive nuclear component. The CO2 rotational relaxation times in the gas phase scale inversely with density in accordance with extended diffusion models of rotational reorientation. The rotational diffusion component of CO2 liquid (τD = 0.34 ps) appears to obey Debye–Stokes–Einstein behavior. The non‐diffusive nuclear responses of the vapor samples exhibit only very modest changes with density and closely resemble the response function of the classical linear free rotor. The dominant, but not exclusive, contribution to the decay of the Raman anisotropy of high‐pressure CO2 gas is inertial motion. The spectral density of the non‐diffusive nuclear response of liquid CO2 is broader and has higher frequency components than the corresponding gas‐phase spectral densities, indicating the relative importance of interaction induced effects. The greater extent of collision‐induced effects is clearly evident for CS2 liquid compared with liquid CO2 when the spectral densities of the non‐diffusive nuclear responses of liquid CO2 and CS2 are compared as a function of reduced frequency. Inertial motion clearly makes a much larger contribution to the birefringence of liquid CO2 than to that of liquid CS2 (at room temperature). Copyright © 2000 John Wiley & Sons, Ltd.

show abstract

Interaction-induced spectra of CO₂

Cited by 21 publications

References 24 publications

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

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

Structure and dynamics of liquid CS2: Going from ambient to elevated pressure conditions

The femtosecond birefringence of CO2: from the high pressure gas to the liquid phase

Contact Info

Product

Resources

About

Interaction-induced spectra of CO2

Cited by 21 publications

References 24 publications

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

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

Structure and dynamics of liquid CS2: Going from ambient to elevated pressure conditions

The femtosecond birefringence of CO2: from the high pressure gas to the liquid phase

Contact Info

Product

Resources

About

Interaction-induced spectra of CO₂