Molecular reorientations in liquid benzene: raman line shapes and 2D NMR relaxation

Gillen, K.T.; Griffiths, James E.

doi:10.1016/0009-2614(72)87096-9

Cited by 115 publications

(36 citation statements)

References 20 publications

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“…This value also falls within the range of the D | values obtained theoretically and experimentally by other authors. 26 The pore size dependences of the D ⊥ and D | are plotted in Figure 3, and Figure 4 shows the ratio D | /D ⊥ as a function of 1/R. One clearly sees that the rotational anisotropy of benzene molecule increases as pore size decreases.…”

Section: Resultsmentioning

confidence: 97%

Raman Study of Vibrational and Rotational Relaxation of Liquid Benzene-d₆ Confined to Nanoporous Silica Glasses

and

Jonáš

1996

J. Phys. Chem.

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Raman spectra of totally symmetric ν 1 , ν 2 bands and three doubly degenerate ν 15 , ν 16 , ν 17 bands of liquid benzene-d 6 confined to porous silica glasses with pore sizes ranging from 14 to 40 Å (average pore radius) were measured at T ) 295 K and atmospheric pressure. The vibrational relaxation rate, τ vib -1 , and the reorientational relaxation time, τ reo (and the perpendicular diffusion constant D ⊥ ), were obtained from the totally symmetric ν 2 band using the standard method. The parallel diffusion constant D | was obtained from the doubly degenerate ν 16 band using a method originally suggested by Tanabe. The results show that τ vib -1 and both D ⊥ and D | are significantly affected by the confinement. As pore size decreases, τ vib -1 increases, while both D ⊥ and D | decrease. The dependence of τ vib -1 and τ reo on the pore size scales as 1/R, indicating a dominant surface interaction effect. Comparing the relative changes of D ⊥ and D | to their bulk liquid values, D | is affected to a lesser extent by the confinement. Consequently, the overall rotation of benzene molecules in nanopores becomes increasingly anisotropic with increasing confinement.

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Section: Resultsmentioning

confidence: 97%

Raman Study of Vibrational and Rotational Relaxation of Liquid Benzene-d₆ Confined to Nanoporous Silica Glasses

and

Jonáš

1996

J. Phys. Chem.

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“…This fact indicates that external self-focusing in benzene occurs under nearly steady-state conditions for ruby laser pulses of approximately 30 ps to 40 ps duration. The orientational relaxation time of benzene of r 0^3 .1ps [40][41][42][43][44][45][46][47] (Table 1) is approximately a factor of ten shorter than the pulse duration.…”

Section: Resultsmentioning

confidence: 99%

Determination of nonlinear refractive indices by external self-focusing

Meier

Penzkofer

1989

Appl. Phys. B

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The nonlinear refractive index of benzene is determined by measuring the reduction of the beam divergence of picosecond ruby laser pulses when passing through a benzene sample. Time-integrated spatial beam profiles give an effective refractive index while time-resolved beam profiles measured with a streak camera allow the determination of the temporal evolution of the nonlinear refractive index. PACS:42.65, 42.65.J At high laser powers the refractive index of materials becomes intensity dependent. The spatial laser beam profile causes a spatial refractive index profile and leads to self-focusing [1][2][3][4][5][6]. The overall beam profile is responsible for whole-beam self-focusing while an intensity modulation of the spatial intensity distribution leads to a beam break-up (small-scale selffocusing) [5][6][7][8]. The combined effects of self-focusing and beam diffraction result in filament formation [1][2][3][4][5][9][10][11][12]. The self-focusing increases the pulse intensity enormously and enhances all nonlinear optical effects [13][14][15][16][17][18][19]. The abrupt rise of nonlinear optical effects is an indication of self-focusing and may be used to determine the self-focusing length. The determination of the nonlinear refractive index from the abrupt rise of nonlinear optical effects is complicated by the fact that either whole-scale self-focusing or small-scale selffocusing may act and the small-scale self-focusing parameters (ripple widths and modulation depths) are difficult to determine.The vagueness of whole-scale or small-scale selffocusing dynamics may be avoided by changing from internal self-focusing (focal point caused by nonlinear refractive index is inside sample) to external selffocusing (focal point is outside sample) [1 ]. In this case the nonlinear refractive index of the sample causes a reduction of the overall beam divergence and the effects of small ripples across the beam profile may be neglected.In our experiments we determine the reduction of beam divergence by comparing the beam diameters (FWHM) of two pulses at a certain distance behind the sample position, where one pulse passes through the sample and the other pulse is bypassed. Our timeresolved measurements of the beam diameters with a streak camera and a two dimensional readout system allow the study of the instantaneous and transient contributions to the nonlinear refractive index [12,18,20]. The effective time-averaged and the time-resolved nonlinear refractive index of benzene are measured with picosecond light pulses of a ruby laser. The reported time-averaged nonlinear refractive index coefficients n 2 of benzene vary by a factor of ten in the region between n 2 = 1.4x 10~2 1 m 2 V~2 and lxlO" 20 m 2 V-2

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“…50 This is reasonable, given that benzene is nonpolar and less affected by the Coulombic field in the ILs.…”

Section: Appendix A: Determination Of Effective Quadrupolar Coupling mentioning

confidence: 93%

“…The QCC eff values are between ∼50 and ∼140 kHz and are significantly smaller than the QCC real values typically obtained for C−D and O−D deuterons. [49][50][51] According to Eq. (A4), the solvent dependence of the QCC eff may contain both the solvent effects on A and QCC real .…”

Section: Appendix A: Determination Of Effective Quadrupolar Coupling mentioning

confidence: 99%

Nuclear magnetic resonance study on rotational dynamics of water and benzene in a series of ionic liquids: Anion and cation effects

Kimura

Yasaka

Nakahara

et al. 2012

The Journal of Chemical Physics

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The rotational correlation times (τ(2R)) for polar water (D(2)O) molecule and apolar benzene (C(6)D(6)) molecule were determined in ionic liquids (ILs) by means of the (2)H (D) NMR spin-lattice relaxation time (T(1)) measurements. The solvent IL was systematically varied to elucidate the anion and cation effects separately. Five species, bis(trifluoromethylsulfonyl)imide (TFSI(-)), trifluoromethylsulfonate (TfO(-)), hexafluorophosphate (PF(6)(-)), chloride (Cl(-)), and formate (HCOO(-)), were examined for the anion effect against a fixed cation species of 1-butyl-3-methyl-imidazolium (bmim(+)). Four species, bmim(+), N-methyl-N-butylpyrrolidinium (bmpy(+)), N,N,N-trimethyl-N-propylammonium (N(1,1,1,3)(+)), and P,P,P-trihexyl-P-tetradecylphosphonium (P(6,6,6,14)(+)), were employed for the cation effect against a fixed anion species of TFSI(-). The τ(2R) ratio of water to benzene, expressed as τ(W/B), was used as a probe to characterize the strength of Coulombic solute-solvent interaction in ILs beyond the hydrodynamic limit based on the excluded-volume effect. The τ(W/B) value was found to strongly depend on the anion species, and the solute dynamics are sensitive not only to the size but also to the chemical structure of the component anion. The cation effect was rather weak, in contrast. The largest and most hydrophobic P(6,6,6,14)(+) cation was exceptional and a large τ(W/B) was observed, indicating a unique solvation structure in [P(6,6,6,14)(+)]-based ILs.

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Molecular reorientations in liquid benzene: raman line shapes and 2D NMR relaxation

Cited by 115 publications

References 20 publications

Raman Study of Vibrational and Rotational Relaxation of Liquid Benzene-d₆ Confined to Nanoporous Silica Glasses

Raman Study of Vibrational and Rotational Relaxation of Liquid Benzene-d₆ Confined to Nanoporous Silica Glasses

Determination of nonlinear refractive indices by external self-focusing

Nuclear magnetic resonance study on rotational dynamics of water and benzene in a series of ionic liquids: Anion and cation effects

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Molecular reorientations in liquid benzene: raman line shapes and 2D NMR relaxation

Cited by 115 publications

References 20 publications

Raman Study of Vibrational and Rotational Relaxation of Liquid Benzene-d6 Confined to Nanoporous Silica Glasses

Raman Study of Vibrational and Rotational Relaxation of Liquid Benzene-d6 Confined to Nanoporous Silica Glasses

Determination of nonlinear refractive indices by external self-focusing

Nuclear magnetic resonance study on rotational dynamics of water and benzene in a series of ionic liquids: Anion and cation effects

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Raman Study of Vibrational and Rotational Relaxation of Liquid Benzene-d₆ Confined to Nanoporous Silica Glasses

Raman Study of Vibrational and Rotational Relaxation of Liquid Benzene-d₆ Confined to Nanoporous Silica Glasses