Li Df

Raman spectra from Symmetric Hydrogen Bonds in Water by High-intensity Laser-induced Breakdown

Raman spectra of ice VII and X were investigated using strong plasma shockwave generated by laser-induced breakdown (LIB) in liquid water. Simultaneously, the occurrence of the hydrogen emission lines of 656 nm (Hα), 486 nm (Hβ), 434 nm (Hγ) and 410 nm (Hδ) was observed. At 5 × 1012 W/cm2 optical power density, the O-H symmetric stretching, translational and librational modes of ice VII and a single peak at 785 cm−1 appeared in the spectra. The band was assigned to the Raman-active O-O mode of the monomolecular phase, which was the symmetric hydrogen bond of cuprite ice X. The spectra indicated that ice VII and X structure were formed, as the trajectory of the strong plasma shockwave passes through the stable Pressure-Temperature range of ice VII and X. The shockwave temperature and pressure were calculated by the Grüneisen model.

The effect of the Fermi resonance on the Raman scattering cross sections of the Fermi doublet ν1 and 2ν2 of liquid carbon disulfide in benzene.

The effect of the Fermi resonance (FR) on the Raman scattering cross sections (RSCSs) of the Fermi doublet ν1, 2ν2 of liquid CS2 in C6H6 using the method of changing the volume concentration of the solution is investigated. We have calculated the RSCSs of the Fermi doublet ν1, 2ν2 using Onsagers theory with the 992 cm(-1) Raman line of C6H6 as the internal standard. The result shows that the RSCS of the ν1 line decreases with decreasing the volume concentration of CS2, while that of the 2ν2 line unexpectedly increases. With decreasing the volume concentration of CS2, two main effects of the solvent effect (SE) and the FR in binary solution that can make the ν1, 2ν2 RSCSs change: the SE, as calculated, reduces both the ν1 and 2ν2 RSCSs; the FR plays a significant role in reducing the ν1 RSCS and enhancing the 2ν2 RSCS. In comparison with our previous investigation [J. Raman Spectrosc. 41 (2010) 776-779], it was found that the stronger the FR is, the more the RSCS of the ν1 decreases and the 2ν2 increases. Thus, we proposed that the result can be best explained by taking into account the effect of the FR on the RSCSs of the Fermi doublet. In addition, this paper also gives an explanation to the experimental results deviating from the theoretical results of the scattering coefficients of CS2 in solvent C6H6 as mentioned in Finis paper.

Raman spectroscopy study on the ν1-2ν2 Fermi resonance of liquid carbon disulfide in binary solutions: Effect of the weak hydrogen bond formation on the Fermi resonance

We have measured the Raman spectra of liquid CS(2) at different volume concentrations in CHCl(3) and CH(2)Cl(2) solutions. With decreasing the volume concentration of CS(2), a noticeable growth in the 2ν(2) band frequency was observed, while the ν(1) band location remained practically unchanged. This asymmetric wavenumber shift phenomenon of the Fermi doublet ν(1) and 2ν(2) of CS(2) has been ascribed to weak, non-conventional hydrogen bonds formed between the CS(2) and the solvent molecules. These weak hydrogen bonds were also responsible for significant decreases in the C-H bond symmetric stretching vibration band frequencies of CHCl(3) and CH(2)Cl(2). The values of the ν(1)-2ν(2) FR parameters of CS(2) in CH(2)Cl(2) and CHCl(3) at different volume concentrations were calculated according to the FR theory. The magnitude of the FR coupling coefficient W of CS(2) increases upon dilution with CH(2)Cl(2) and CHCl(3), indicating that the vibrational anharmonicity is relatively sensitive to variations in the weak hydrogen bonding. Compared with the changing tendencies of Fermi coupling coefficient W of CS(2) in CH(2)Cl(2) and CHCl(3) at different volume concentrations, we discussed the effect of the weak hydrogen bond formation on the FR and the asymmetric wavenumber shift phenomenon of the Fermi doublet ν(1) and 2ν(2) of CS(2).

High-pressure Raman study of Terephthalonitrile☆

The in situ high-pressure Raman spectra of Terephthalonitrile (TPN) have been investigated from ambient to 12.6GPa at room temperature. All the fundamental vibrational modes of TPN at ambient were assigned based on the first-principle calculations. A detailed Raman spectroscopy analysis revealed that TPN underwent a phase transition at ~5.3GPa. The frequencies of the TPN Raman peaks increase with increasing the pressure which can be attributed to the reduction in the interatomic distances and the escalation of effective force constants. The intensity of the C-C-C ring-out-plane deformation mode increases gradually as the frequency remains almost constant during the compression which can be explained by the existence of π-π interactions in TPN molecules. Additionally, the pressure-induced structural changes of TPN on the Fermi resonance between the C≡N out-of-plane vibration mode and the C-CN out-of-plane vibration mode have been analyzed.

Stimulated Raman scattering from sulfur-II produced by laser decomposition of liquid carbon disulfide.

Stimulated Raman scattering (SRS) of sulfur-II (S-II) phase was investigated by laser decomposition of liquid carbon disulfide. As a matter of fact, above a threshold of the laser intensity, it is suggested that a strong shock wave is generated in the liquid carbon disulfide, which is decomposed owing to the induced high dynamic pressure and temperature. One bending mode E frequency at 289 cm(-1) and one symmetric stretching mode A1 frequency at 490 cm(-1) of S-II phase were observed. The SRS spectra indicated that S-II structure is formed by laser decomposition, as the strong shock wave generates the stable pressure-temperature range of S-II phase. The dynamic high-pressure and static-electric field generated by laser-induced breakdown results in the softening A1 mode becoming more hardened.