Molecular Motions in CCl4: Light Scattering and Infrared Absorption

Bucaro, J. A.; Litovitz, T. A.

doi:10.1063/1.1676617

Cited by 57 publications

(7 citation statements)

References 9 publications

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“…Although the bands are very weak, the baseline-corrected reduced isotropic spectra in Figures and show evidence for five statistically significant Raman active peaks at 25 °C, and three at 80 °C, which can be resolved by the deconvolution method described above. The low frequency region below ∼250 cm –1 is characteristic of librational modes that reflect the structure and dynamics of water, and as a result, we conclude that the weak band at 200 ± 20 cm –1 is due to hydration effects and that it can be excluded as a species. ,− The two distinctive peaks at 297 ± 3 and 247 ± 3 cm –1 occur in the frequency range identified by the ab initio calculations for copper species, described below.…”

Section: Resultsmentioning

confidence: 59%

Raman and ab Initio Investigation of Aqueous Cu(I) Chloride Complexes from 25 to 80 °C

et al. 2013

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Temperature-dependent Raman studies of aqueous copper(I) chloride complexes have been carried out up to 80 °C, along with supporting ab initio calculations for the species [CuCl(n)(H2O)m](1-n), n = 0-4 and hydration numbers m = 0-6. Normalized reduced isotropic Raman spectra were obtained from perpendicular and parallel polarization measurements, with perchlorate anion, ClO4(-), as an internal standard. Although the Raman spectra were not intense, spectra could be corrected by solvent baseline subtraction, to yield quantitative reduced molar scattering coefficients for the symmetric vibrational bands at 297 ± 3 and 247 ± 3 cm(-1). The intensity variations of these bands with concentration and temperature provided strong evidence that these arise from the species [CuCl2](-) and [CuCl3](2-), respectively. The results from ab initio calculations using density functional theory predict similar relative peak positions and intensities for the totally symmetric Cu-Cl stretching bands of the species [CuCl2(H2O)6](-) and [CuCl3(H2O)6](2-), in which the water is coordinated to the chloride ions. A less intense Raman band at 350 ± 10 cm(-1) is attributed to the symmetric Cu-Cl stretching mode of hydrated species [CuCl(H2O)](0) with six waters of hydration. Temperature- and concentration-independent quantitative Raman molar scattering coefficients (S) are reported for the [CuCl2](-) and [CuCl3](2-)species.

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Section: Resultsmentioning

confidence: 59%

Raman and ab Initio Investigation of Aqueous Cu(I) Chloride Complexes from 25 to 80 °C

et al. 2013

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“…The line shape functions in eqs 19 and 20 have been used previously to describe the OHD-RIKES 16d and SGS 31 spectra of other liquids. The line shape function I BL (Δω) was originally introduced by Bucaro and Litovitz to account for collision-induced contributions to DLS spectra in liquids. However, in this analysis, I BL (Δω) is just treated as an empirical fitting function.…”

Section: Analysis and Discussionmentioning

confidence: 99%

Structure and Intermolecular Dynamics of Liquids: Femtosecond Optical Kerr Effect Measurements in Nonpolar Fluorinated Benzenes

1997

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A comparative study of the collective polarizability anisotropy dynamics of benzene, 1,3,5-trifluorobenzene, and hexafluorobenzene was carried out by using optical heterodyne-detected Raman-induced Kerr effect spectroscopy (OHD-RIKES) with 45 fs laser pulses. The OHD-RIKES data were analyzed by using a modeldependent approach and a Fourier transform approach, which yields a spectral density for the liquid. From an analysis of the long-time tails, collective reorientation times of 2.45 ( 0.06, 9.05 ( 0.10, and 13.5 ( 0.1 ps were obtained respectively for C 6 H 6 , 1,3,5-C 6 F 3 H 3 , and C 6 F 6 . The spectral densities are narrower for 1,3,5-C 6 F 3 H 3 and C 6 F 6 than for C 6 H 6 by roughly a factor of 2. Information about the intermolecular vibrational modes of the liquid is contained in the reduced spectral density which is obtained by subtracting the tailmatched diffusive reorientational response from the OHD-RIKES data. In the case of C 6 H 6 and C 6 F 6 , the intermolecular spectral density can be decomposed into at least two broad overlapping bands. In contrast, the intermolecular spectral density for 1,3,5-C 6 F 3 H 3 is characterized by a single band. These spectra are rationalized in terms of the librational dynamics of perpendicular dimers in liquid C 6 H 6 and C 6 F 6 and parallel dimers in liquid 1,3,5-C 6 F 3 H 3 .

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“…18,19 The associated collisioninduced dipole moments were estimated to be in the order of 0.1-0.2 D, or about 0.25-0.5 a.u.-a very strong dipole moment if compared to other well-known induced dipoles. 18,19 The associated collisioninduced dipole moments were estimated to be in the order of 0.1-0.2 D, or about 0.25-0.5 a.u.-a very strong dipole moment if compared to other well-known induced dipoles.…”

Section: A Frame-distortion-induced Dipoles and Spectramentioning

confidence: 99%

“…A strong dependence of the rotation-induced corrections on the rotational state is again noted. 19 19 …”

Section: B Other Known Manifestationsmentioning

confidence: 99%

Infrared absorption by collisional CH4+X pairs, with X=He, H2, or N2

Buser

Frommhold

2004

The Journal of Chemical Physics

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Existing measurements of the collision-induced rototranslational absorption spectra of gaseous mixtures of methane with helium, hydrogen, or nitrogen are compared to theoretical calculations, based on refined multipole-induced and dispersion force-induced dipole moments of the interacting molecular pairs CH4-He, CH4-H2, and CH4-N2. In each case the measured absorption exceeds the calculations substantially at most frequencies. We present the excess absorption spectra, that is the difference of the measured and the calculated profiles, of these supramolecular CH4-X systems at various gas temperatures. The excess absorption spectra of CH4-X pairs differ significantly for each choice of the collision partner X, but show common features (spectral intensities and shape) at frequencies from roughly 200 to 500 cm(-1). These excess spectra seem to defy modeling in terms of ad hoc exchange force-induced dipole components attempted earlier. We suggest that besides the dipole components induced by polarization in the electric molecular multipole fields and their gradients, and by exchange and dispersion forces, other dipole induction mechanisms exist in CH4-X complexes that presumably are related to collisional distortion of the CH4 molecular frame.

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Molecular Motions in CCl4: Light Scattering and Infrared Absorption

Cited by 57 publications

References 9 publications

Raman and ab Initio Investigation of Aqueous Cu(I) Chloride Complexes from 25 to 80 °C

Raman and ab Initio Investigation of Aqueous Cu(I) Chloride Complexes from 25 to 80 °C

Structure and Intermolecular Dynamics of Liquids: Femtosecond Optical Kerr Effect Measurements in Nonpolar Fluorinated Benzenes

Infrared absorption by collisional CH4+X pairs, with X=He, H2, or N2

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