Sun Cheng-Lin

Investigation of hydrogen bonding in neat dimethyl sulfoxide and binary mixture （dimethyl sulfoxide water） by concentration-dependent Raman study and ab initio calculation

In this study, our vibrational spectroscopic analysis is made on hydrogen-bonding between dimethyl sulfoxide and water comprises both experimental Raman spectra and ab initio calculations on structures of various dimethyl sulfoxide/water clusters with increasing water content. The Raman peak position of the v(S=O) stretching mode of dimethyl sulfoxide serves as a probe for monitoring the degree of hydrogen-bonding between dimethyl sulfoxide and water. In addition, the two vibrational modes, namely, the CH3 symmetric stretching mode and the CH3 asymmetric stretching mode have been analysed under different concentrations. We relate the computational results to the experimental vibrational wavenumber trends that are observed in our concentration-dependent Raman study. The combination of experimental Raman data with ab initio calculation leads to a better knowledge of the nature of the hydrogen bonding and the structures of the hydrogen-bonded complexes studied.

Investigation of inter-molecular hydrogen bonding in the binary mixture (acetone + water) by concentration dependent Raman study and ab initio calculations

This paper reports that vibrational spectroscopic analysis on hydrogen-bonding between acetone and water comprises both experimental Raman spectra and ab initio calculations on structures of various acetone/water complexes with changing water concentrations. The optimised geometries and wavenumbers of the neat acetone molecule and its complexes are calculated by using ab initio method at the MP2 level with 6–311+G(d,p) basis set. Changes in wavenumber position and linewidth (fullwidth at half maximum) have been explained for neat as well as binary mixtures with different mole fractions of the reference system, acetone, in terms of intermolecular hydrogen bonding. The combination of experimental Raman data with ab initio calculation leads to a better knowledge of the concentration dependent changes in the spectral features in terms of hydrogen bonding.

EFFECT OF OPTICAL FIBER LOSS ON RESONANCE RAMAN SPECTRA OF SAMPLES WITH LOW CONCENTRATION

The resonance Raman effect which is produced in a liquid-core optical fiber can enhance the Raman spectral intensity 109 times. The optimum length of the optical fiber depends on the sample concentration, modal absorption coefficient, scattering coefficient, coupling coefficient, and molar absorptivity. A sample with a lower concentration is preferred. We obtained the Raman spectra of samples with low concentrations 1×10−15 mol/L(I2 in CS2) and 0.8×10−16 mol/L (β-carotene in CS2).

A polyene chain of canthaxanthin investigated by temperature-dependent resonance Raman spectra and density functional theory （DFT） calculations

We report on a temperature-dependent resonance Raman spectral characterization of the polyene chain of canthaxanthin. It is observed that all vibrational intensities of the polyene chain are inversely proportional to temperature, which is analyzed by the resonance Raman effect and the coherent weakly damped electron/lattice vibrations. The increase in intensity of the CC overtone/combination relative to the fundamental with temperature decreasing is detected and discussed in terms of electron/phonon coupling and the activation energy Uop. Moreover, the polyene chain studies using the density functional theory B3LYP/6-31G* level reveal a prominent peak at 1525 cm−1 consisting of two closely spaced modes that are both dominated by C=C stretching coordinates of the polyene chain.

High-pressure-activated carbon tetrachloride decomposition

The pressure-induced molecular dissociation as one of the fundamental problems in physical sciences has aroused many theoretical and experimental studies. Here, using a newly developed particle swarm optimization algorithm, we investigate the high-pressure-induced molecular dissociation. The results show that the carbon tetrachloride (CCl4) is unstable and dissociates into C2Cl6 and Cl2 under approximately 120 GPa and more. The dissociation is confirmed by the lattice dynamic calculations and electronic structure of the Pa3 structure with pressure evolution. The dissociation pressure is far larger than that in the case of high temperature, indicating that the temperature effectively reduces the activation barrier of the dissociation reaction of CCl4. This research improves the understanding of the dissociation reactions of CCl4 and other halogen compounds under high pressures.

The effect of an anti-hydrogen bond on Fermi resonance: A Raman spectroscopic study of the Fermi doublet ν1−ν12 of liquid pyridine

The effects of an anti-hydrogen bond on the ν1−ν12 Fermi resonance (FR) of pyridine are experimentally investigated by using Raman scattering spectroscopy. Three systems, pyridine/water, pyridine/formamide, and pyridine/carbon tetrachloride, provide varying degrees of strength for the diluent-pyridine anti-hydrogen bond complex. Water forms a stronger anti-hydrogen bond with pyridine than with formamide, and in the case of adding non-polar solvent carbon tetrachloride, which is neither a hydrogen bond donor nor an acceptor and incapable of forming a hydrogen bond with pyridine, the intermolecular distance of pyridine will increase and the interaction of pyridine molecules will reduce. The dilution studies are performed on the three systems. Comparing with the values of the Fermi coupling coefficient W of the ring breathing mode ν1 and triangle mode ν12 of pyridine at different volume concentrations, which are calculated according to the Bertran equations, in three systems, we find that the solution with the strongest anti-hydrogen bond, water, shows the fastest change in the ν1−ν12 Fermi coupling coefficient W with the volume concentration varying, followed by the formamide and carbon tetrachloride solutions. These results suggest that the stronger anti-hydrogen bond-forming effect will cause a greater reduction in the strength of the ν1−ν12 FR of pyridine. According to the mechanism of the formation of an anti-hydrogen bond in the complexes and the FR theory, a qualitative explanation for the anti-hydrogen bond effect in reducing the strength of the ν1−ν12 FR of pyridine is given.

The stimulated Raman scattering competition between solute and solvent in Rhodamine B solution

The competition between the stimulated resonance Raman scattering (SRRS) of Rhodamine B (RhB) and the stimulated Raman scattering (SRS) of ethanol (C2H5OH) is observed at the RhB in C2H5OH solution. For different concentrations of the solution, the peak wavelengths of the SRRS, the amplified spontaneous emission (ASE), the fluorescence and the absorption of RhB are different. The SRRS of RhB and the SRS of C2H5OH are simultaneously generated when the concentration of the solution is 10−5 mol/L and the energy of the excitation laser is 20.4 mJ. Otherwise, only either the SRRS of RhB or the SRS of C2H5OH is generated. The SRRS can be amplified by the ASE gain when the SRRS is near the peak of the ASE, and the peak wavelength of the SRRS coincides with the wavelength of the maximal intensity ASE.

Difference in effect of temperature on absorption and Raman spectra between all-trans-β-carotene and all-trans-retinol

Temperature dependencies (81 °C–18 °C) ofvisible absorption and Raman spectra of all-trans-β-carotene and all-trans-retinol extremely diluted in dimethyl sulfoxide are investigated in order to clarify temperature effects on different polyenes. Their absorption spectra are identified to be redshifted with temperature decreasing. Moreover, all-trans-β-carotene is more sensitive to temperature due to the presence of a longer length of conjugated system. The characteristic energy responsible for the conformational changes in all-trans-β-carotene is smaller than that in all-trans-retinol. Both of the Raman scattering cross sections increase with temperature decreasing. The results are explained with electron—phonon coupling theory and coherent weakly damped electron—lattice vibrations model.

Relationship between Fermi Resonance and Solvent Effects

We theoretically and experimentally study the relationship between Fermi resonance and solvent effects and investigate the Fermi resonance of p-benzoquinone and cyclopentanone in different solvents and the Fermi resonance of CS2 in C6H6 at different concentrations. Also, we investigate the Fermi resonance of C6H6 and CCl4 in their solution at different pressures. It is found that solvent effects can be utilized to search Fermi resonance parameters such as coupling coefficient and spectral intensity ratio, etc., on the other hand, the mechanism of solvent effects can be revealed according to Fermi resonance at high pressure.