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Theoretical investigations are performed on mechanism and kinetics of the reactions of ethyl radical C2H5 with NCO radical. The electronic structure information of the PES is obtained at the B3LYP/6-311++G(d,p) level of theory, and the single-point energies are refined by the CCSD(T)/6-311+G(3df,2p) level of theory. The rate constants for various product channels of the reaction in the temperature range of 200-2000K are predicted by performing VTST and RRKM calculations. The calculated results show that both the N and O atoms of the NCO radical can attack the C atom of C2H5 via a barrierless addition mechanism to form two energy-rich intermediates IM1 C2H5NCO(89.1 kcal/mol) and IM2 C2H5OCN(64.7 kcal/mol) on the singlet PES. Then they both dissociate to produce bimolecular products P1 C2H4 + HOCN and P2 C2H4 + HNCO. At high temperatures or low pressures, the reaction channel leading to bimolecular product P2 is dominant and the channel leading to P1 is the secondary, while, at low temperatures and high pressures, the collisional stabilization of the intermediate plays an important role and as a result IM2 becomes the primary product. The present results will enrich our understanding of the chemistry of the NCO radical in combustion processes. [ABSTRACT FROM AUTHOR]

The research group prepared the high-performance slag nanocrystal glass ceramics by utilizing the valuable elements of the wastes in the Chinese Bayan Obo which are characterized by their symbiotic or associated existence. In this paper, inductively coupled plasma emission spectroscopy (ICP), X-ray diffraction (XRD), Raman spectroscopy (Raman) and scanning electron microscopy (SEM) are all used in the depth analysis for the composition and structure of the samples. The experiment results of ICP, XRD and SEM showed that the principal crystalline phase of the slag nanocrystal glass ceramics containing rare earth elements is diopside, its grain size ranges from 45 to 100 nm, the elements showed in the SEM scan are basically in consistent with the component analysis of ICP. Raman analysis indicated that its amorphous phase is a three-dimensional network structure composed by the structural unit of silicon-oxy tetrahedron with different non-bridging oxygen bonds. According to the further analysis, we found that the rare earth microelement has significant effect on the network structure. Compared the nanocrystal slag glass ceramic with the glass ceramics of similar ingredients, we found that generally, the Raman band wavenumber for the former is lower than the later. The composition difference between the glass ceramics and the slag nanocrystal with the similar ingredients mainly lies on the rare earth elements and other trace elements. Therefore, we think that the rare earth elements and other trace elements remains in the slag nanocrystal glass ceramics have a significant effect on the network structure of amorphous phase. The research method of this study provides an approach for the relationship among the composition, structure and performance of the glass ceramics.

In the present paper, nanocrystalline glass-ceramic of CaO-MgO-Al2O3-SiO2 system was produced by melting method. The CaO-MgO-Al2O3-SiO2 nanocrystalline glass-ceramic was measured by Raman spectroscopy in the temperature range from -190 to 310 degrees C in order to study the effect of temperature on the structure of this system nanocrystalline glass-ceramics. The results showed that different non-bridge oxygen bond silicon-oxygen tetrahedron structural unit changes are not consistent with rising temperature. Further analyses indicated that: the SiO4 tetrahedron with 2 non-bridged oxygen (Q2), the SiO4 tetrahedron with 3 non-bridged oxygen (Q(1)), which are situated at the edge of the 3-D SiO4 tetrahedrons network, and the SiO4 tetrahedron with 4 non-bridged oxygen (Q(0)), which is situated outside the 3-D network all suffered a significant influence by the temperature change, which has been expressed as: shifts towards the high wave-number, increased bond force constants, and shortened bond lengths. This paper studied the influence of temperature on CMAS system nanocrystalline glass-ceramics using variable temperature Raman technology. It provides experiment basis to the research on external environment influence on CMAS system nanocrystalline glass-ceramics materials in terms of structure and performance. In addition, the research provides experimental basis for controlling the expansion coefficient of nanocrystalline glass-ceramic of CaO-MgO-Al2O3-SiO2 system.

In the present paper, DMSO/H2O mixture with the ratio of volume 1:1 was measured in the cooling process by Raman spectroscopy, and the Raman assignments was made to the DMSO molecular and water molecular. The results showed that the behavior between intra-molecular hydrogen bonds and inter-molecular hydrogen bonds of DMSO and water leads to the change in the Raman spectra of the S==O stretching vibration of DMSO and the O--H stretching vibration of water. Further analysis showed that the hydrogen bond between DMSO and water was enhanced in the course of temperature decreasing process (27 to -30 degrees C), and the intramolecular hydrogen bonds between water and water replaced the intermolecular hydrogen bonds of DMSO and water in the course of temperature decreasing process (-30 to -60 degrees C). The research provides experimental basis for hydrogen bonding theory in aqueous solution.

In the present paper, studies on in-situ Raman spectra at high pressure up to 12.85 Gpa were performed on beta-carotene using a diamond anvil cell (DAC), and the effects of pressure on the characteristic peaks and pi-electron delocalization of beta-carotene were discussed. The results showed that Raman frequencies of the main characteristic peaks of beta-carotene shifted to high wavenumber with the increase in pressure. The relation between pressure and the three main characteristic peaks of beta-carotene was given as follows: nu1, (C==C) = 4. 74P + 1511.4, w (C-C) = 2.55P + 157.6 and nu3 (CH3) = 2.25P + 1011.3. Under the pressure of 5.38 GPa, Raman spectrum of nu1 + nu2 sum frequency of beta-carotene was subjected to cleavage. Fuethermore, the degree of relectron decolization was reduced with the increase in pressure, leading to C==C double bond more compressible than C-C bond on the main chain of beta-carotene.

In the present paper, the frequency shift and line widths of acetonitrile/H2O, DMSO/H2O and acetone/H2O aqueous binary solutions at different concentration were measured by Raman spectroscopy. The experimental results were analyzed by mixture model and empirical formula of line widths. The results show that the stronger the hydrogen bond interaction, the greater the line widths of Raman spectra in the three aqueous binary solutions; the line width of Raman spectra not only is affected by concentration fluctuation, but also is affected by hydrogen bond. In addition, the experimental data points are again nicely fitted using the empirical formula.

Lycopene and beta-carotene are two important nutritional components in tomato. The main Raman spectrum group of lycopene and beta-carotene abundant in tomato is identical and difficult to be distinguished through fundamental frequency. With excitation wavelength of 514.5 nm, the excited light was just present in the half width range of the main absorption bands of Lycopene and beta-carotene, so the resonance Raman effect can occur. Based on resonance Raman spectra, by on-body measuring the second harmonic of stretching vibration of carbon-carbon conjugated double bond in lycopene and beta-carotene, the content of lycopene and beta-carotene can be obtained according to the integrated intensity of each component calculated by software. And this provides a method for on-body determining the content of the components with the homologous group.