Gao Shu-Qin

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).

Phase Transition in CCl4 under Pressure: a Raman Spectroscopic Study

High-pressure Raman studies at room temperature are performed on CCl4 up to 13 GPa. The Raman bands of the internal modes (v2, v4 and v1) show entirely positive pressure dependence. The slopes dω/dP of the internal modes exhibit two sudden changes at 0.73 GPa and 7.13 GPa, respectively. A new lower frequency mode (225 cm−1) appears at 3.03 GPa, and the splitting of v2, v3 and v4 occurs at about 7.13 GPa. Moreover, Raman spectra of Fermi resonance show that the relative position of the v1 + v4 combination and the v3 fundamental firstly interchanges corresponding to that at ambient pressure, then the v1 + v4 combination disappears in the gradual process of compression. It is indicated that the pressure-induced phase transition from CCl4 II to CCl4 III occurs at 0.73 GPa, and CCl4 III undergoes a transition to CCl4 IV below 3.03 GPa. Further CCl4 IV transforms in a new high-pressure phase at about 7.13 GPa, and the symmetry of the new high-pressure phase is lower than that of CCl4 IV. All the transitions are reversible during decompression.

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.

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.

Excitonic Coupling between B and Q Transitions in Porphyrin Aggregates

The properties of meso-tetraphenylporphine (TPP) aggregates formed in acidic aqueous-organic solutions are investigated by UV-vis spectroscopy. According to the absorption spectra, the Q band absorption of the aggregated TPP shows red shift and intensity enhancement, and a model that includes the participation of water molecules in a porphyrin aggregation complex is proposed, then a qualitative explanation based on Goutermans excition coupling theory is presented. Calculations including eigenenergies, eigenstates and the transition dipole strength of the coupled states are carried out.

Influence of Temperature on Stimulated Raman Scattering in Single-Mode Silica Fibre

One piece of single-mode silica fibre is used to study of temperature characteristics of stimulated Raman scattering (SRS), additional peaks (double-humped) are observed at both sides of pump light and 1st-order Stokes light in the experiment. The frequency shift of the double-humped is calculated by stimulated Four–Photon mixing (SFPM) phase matching theory, the result is consistent with the frequency shift of this experiment. Simultaneously, the experimental conditions accord with the theoretical calculation of effective coherence length. We indicate that the double-humped phenomenon is caused by SFPM. The intensity of double-humped is first increased, then decreased and finally disappeared as the temperature increases. This phenomenon has been explained theoretically.