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Absolute Orientation of Molecules with Competing Hydrophilic Head Groups at the Air/Water Interface Probed with Sum Frequency Generation Vibrational Spectroscopy

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Chinese Journal of Chemical Physics 2009年第2期22卷 197-203页

作者： feng Wang zhi Huang zhi-feng cui Hong-fei Wang Department of Physics Anhui Normal University Wuhu 241000 China Beijing National Laboratory for Molecular Sciences State Key Laboratory of Molecular Reaction Dynamics Institute of Chemistry Chinese Academy of Sciences Beijing 100190 China

The constructive or destructive spectral interference between the molecular groups oriented up and down at the interface in the sum-frequency generation （SFG） spectra provides a direct measurement of the absolute orientation of these molecular groups. This simple approach can be employed to interrogate absolute molecular orientations other than using the complex absolute phase measurement in the SFG studies. We used the -CN group in the p-cyanophenol （PCP） molecule as the internal phase standard, and we measured the phases of the SFG fields of the -CN groups in the 3,5-dimethyl-4-hydroxy-benzonitrile （35DMHBN） and 2,6-dimethyl-4-hydroxy-benzonitrile （26DMHBN） at the air/water interface by measuring the SFG spectra of the aqueous surfaces of the mixtures of the PCP, 35DMHBN, and 26DMHBN solutions. The results showed that the 35DMHBN had its -CN group pointing into the aqueous phase; while the 26DMHBN, similar to the PCP, had its -CN group pointing away from the aqueous phase. The tilt angles of the -CN group for both the 35DMHBN and 26DMHBN molecules at the air/water interface were around 25°-45° from the interface normal. These results provided insights on the understanding of the detailed balance of the competing factors, such as solvation of the polar head groups, hydrogen bonding and hydrophobic effects, etc., on influencing the absolute molecular orientation at the air/water interface.

关键词： Sum frequency generation vibrational spectroscopy Air/water interface Molecule orientation p-cyanophenol

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Temperature and electron density of soil plasma generated by LA-FPDPS

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Frontiers of physics 2012年第6期7卷 721-727页

作者： Xia-Fen Li Wei-Dong Zhou zhi-feng cui The Institute of Information Optics Zhejiang Normal UniversityJinhua 321004China Department of Physics Anhui Normal UniversityWuhu 241000China

Electron temperature and electron number density are important parameters in the characterization of plasma. In this paper the electron temperature and electron number density of soil plasma generated by laser ablation combined with nanosecond discharge spark at different discharge voltages have been studied. Saha-Boltzmann plot and Stark broadening are used to determine the temper- ature and electron number density. It is proved that local thermal equilibrium is fulfilled in the nanosecond spark enhanced plasma. The enhanced optical emission, signal to noise ratio and the stability in term of the relative standard deviation of signal intensity at different spark voltages were investigated in detail. A relative stable discharge process was observed with use of a 10 kV discharge voltage under the carried experimental configuration.

关键词： laser ablation fast pulse discharge plasma spectroscopy (LA-FPDPS) local thermodynamic equilibrium (LTE) electron temperature electron number density discharge voltage

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Quantitative Interpretation of Polarization SFG Vibrational Spectra of Air/Methanol Interface

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Chinese Journal of Chemical Physics 2006年第3期19卷 187-189页

作者： Hui Wu Wen-kai Zhang Wei Gan zhi-feng cui Hong-fei Wang Department of Physics Anhui Normal University Wuhu 241000 China State Key Laboratory of Molecular Reaction Dynamics Institute of Chemistry Chinese Academy of Sciences Beijing 100080China

Even though in IR and Raman spectra of liquid methanol there is always an apparent feature for the asymmetric stretching mode of the CH3 group around 2970 cm^-1, this feature has not been observed in the Sum Frequency Generation Vibrational Spectroscopy （SFG-VS） in any polarizations from the air/methanol interface. Here we present a treatment based on a corrected bond additivity model to quantitatively interpret the SFG-VS of the air/methanol interface from the IR and Raman spectra of liquid methanol.

关键词： Sum frequency generation Bond additivity model Raman polarizability

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Experimental and Theoretical Study on p-Chlorofluorobenzene in the S0,S1 and D0 States

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Chinese Journal of Chemical Physics 2020年第4期33卷 401-410,I0001页

作者： Jia-nan Fan Ting-ting cui Zheng-bo Qin Xian-feng Zheng zhi-feng cui Anhui Province Key Laboratory of Optoelectric Materials Science and Technology Department of PhysicsAnhui Normal UniversityWuhu 241000China

The geometric structures and vibration frequencies of para-chlorofluorobenzene(p-Cl FPh)in the first excited state of neutral and ground state of cation were investigated by resonanceenhanced multiphoton ionization and slow electron velocity-map *** infrared spectrum of S0 state and absorption spectrum for S1←S0 transition in p-Cl FPh were also *** on the one-color resonant two-photon ionization spectrum and two-color resonant two-photon ionization spectrum,we obtained the adiabatic excited-state energy of p-Cl FPh as 36302±4 cm^-*** the two-color resonant two-photon ionization slow electron velocity-map imagin spectra,the accurate adiabatic ionization potential of p-Cl FPh was extrapolated as 72937±8 cm^-1 via threshold ionization *** addition,FranckCondon simulation was performed to help us confidently ascertain the main vibrational modes in the S1 and D0 ***,the mixing of vibrational modes between S0→S1 and S1→D0 has been analyzed.

关键词： Resonance-enhanced multiphoton ionization Slow electron velocity-map imaging Duschinsky mixing para-Chlorofluorobenzene

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Measurement of Photoionization Cross Sections of the Excited States of Titanium

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Chinese Journal of Chemical Physics 2009年第6期22卷 615-620,J0002页

作者： Jia-jun Yang Xing-yong Hu Hong-xia Wu Jian-mei Fan Ran Cong Yi Cheng Xue-han Ji Guan-xin Yao Xian-feng Zheng zhi-feng cui Institute of Atomic and Molecular Physics Anhui Normal University Wuhu 242000 China

Resonance-enhanced multiphoton ionization of the titanium atoms has been investigated in the 293 321 nm wavelength. We couple a laser-ablated metal target into a molecular beam to produce free atoms. Ions produced from photoionization of the neutral atoms are monitored by a home-built time-of-flight mass spectrometer. Photoionization cross sections of the excited states of Ti I were deduced from the dependence of the ion signal intensity on the laser intensity for photon energies close to the ionization threshold. The values obtained range from 0.2 Mb to 6.0 Mb. No significant isotope-dependence was found from measurements of the photoionization cross sections of ^46Ti, ^47Ti, and ^48Ti.

关键词： Photoionization cross section Excited state Titanium

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Reduction of dinitrogen to ammonia on doped three-atom clusters Nb_(2)M(M=Sc to Cu & Y to Ag)

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Rare Metals 2024年第8期43卷 3810-3818页

作者： Ran Cheng Chao-Nan cui zhi-Xun Luo Beijing National Laboratory for Molecular Science(BNLMS) State Key Laboratory for Structural Chemistry of Unstable and Stable SpeciesInstitute of ChemistryChinese Academy of SciencesBeijing 100190China School of Chemical Science University of Chinese Academy of SciencesBeijing 100049China

Catalytic reduction of dinitrogen to ammonia under mild conditions remains an attractive topic for the purpose of lowering energy ***-atom metal clusters have been proved an ideal model to explore highly efficient catalysts taking advantage of unique geometric/electronic structures and cooperative active *** a study of N2 activation and reduction on seventeen bimetallic Nb_2M(M=Sc to Cu,and Y to Ag) clusters was *** key processes for ammonia fixation(namely nitrogen activation,hydrogenation,and ammonia desorption) are fully studied,and three preferred systems(Nb_2Ni,Nb_2Rh and Nb_2Pd) are highlighted with outstanding catalytic *** d-σ and d-π~* orbital hybridizations between these metal clusters and N_(2) were demonstrated and the internal association with the N≡N bond activation was *** examining the ammonia synthesis on four chosen Nb_(2)M clusters(M=Fe,Ni,Rh and Pd),it can be elucidated that the distal pathway is more favorable than the alternative pathway in these *** work not only clarifies the N_(2) reduction on the bimetallic Nb_(2)M clusters,but also guides efficient bimetallic catalyst design.

关键词： Three-atom cluster catalysis Three-criteria strategy Nitrogen fixation Ammonia synthesis Theoretical calculations

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TR-ESR Investigation on Reaction of Vitamin C with Excited Triplet of 9,10-phenanthrenequinone in Reversed Micelle Solutions

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Chinese Journal of Chemical Physics 2011年第2期24卷 150-154,I0003页

作者：许新胜史蕾刘毅季学韩崔执凤安徽师范大学原子与分子物理研究所芜湖241000

Time-resolved electron spin resonance has been used to study quenching reactions between the antioxidant Vitamin C （VC） and the triplet excited states of 9,10-phenanthrenequinone （PAQ） in ethylene glycol-water （EG-H2O） homogeneous and inhomogeneous reversed micelle solutions. Reversed micelle solutions were used to be the models of physiological environment of biological cell and tissue. In PAQ/EG-H2O homogeneous solution, the excited triplet of PAQ （3PAQ＊） abstracts hydrogen atom from solvent EG. In PAQ/VC/EG-H2O solution, 3pAQ＊ abstracts hydrogen atom not only from solvent EG but also from VC. The quenching rate constant of 3pAQ＊ by VC is close to the diffusion-controlled value of 1.41 × 108 L/（mol.s）. In hexadecyltrimethylammonium bromide （CTAB）/EG-H2O and aerosol OT （AOT）/EG- H2O reversed micelle solutions, 3pAQ＊ and VC react around the water-oil interface of the reversed micelle. Exit of 3pAQ＊ from the lipid phase slows down the quenching reaction. For Triton X-100 （TX-100）/EG-H2O reversed micelle solution, PAQ and VC coexist inside the hydrophilic polyethylene glycol core, and the quenching rate constant of 3pAQ＊ by VC is larger than those in AOT/EG-H2O and CTAB/EG-H2O reversed micelle solutions, even a little larger than that in EG-H2O homogeneous solution. The strong emissive chemically induced dynamic electron polarization of As＇- resulted from the effective TM spin polarization transfer in hydrogen abstraction of 3pAQ＊ from VC.

关键词： 9,10-phenanthrenequinone Vitamin C Time-resolved electron spin resonance Reversed micelle

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Influence of ammonium sulfate on the corrosion behavior of AZ31 magnesium alloy in chloride environment

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Journal of Magnesium and Alloys 2024年第3期12卷 1082-1101页

作者： feng Ge Zhongyu cui Yue Liu Li Lei Xin Wang Hongzhi cui School of Materials Science and Engineering Ocean University of ChinaQingdao 266100China Beijing National Innovation Institute of Lightweight Ltd.Beijing 101499China

Electrochemical corrosion of AZ31 magnesium alloy in the NH_(4)^(+)-SO_(4)2−-Cl−environment is *** of NH_(4)^(+)overshadows that of Cl−as the(NH_(4))_(2)SO_(4) concentration is 0.005 M or higher,yielding an evolution from localized corrosion to uniform *** effect of NH_(4)^(+)can be attributed to that(i)NH_(4)^(+)dissolves the inner MgO and hinders the precipitation of Mg(OH)_(2) and(ii)the buffering ability of NH_(4)^(+)provides H+,enhances the hydrogen evolution,and expedites the corrosion *** latter is demonstrated as the dominant factor with the results in unbuffered and buffered *** severe corrosion and hydrogen process in NH_(4)^(+)-containing solution results in a high Hads coverage and yields an inductive loop within the low ***,SO_(4)^(2−)is helpful in generating cracked but partially protective corrosion products,while Cl−could broaden the corrosion area beneath the corrosion product.

关键词： Magnesium alloy Ammonium corrosion Electrochemical kinetic parameter Anodic dissolution.

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Asymmetric Hydrogenation of Phenanthridines with Chiral Boranes

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Chinese Journal of Chemistry 2024年第6期42卷 631-635页

作者： Guangyu cui Xiangqing feng Haifeng Du Beijing National Laboratory for Molecular Sciences CAS Key Laboratory of Molecular Recognition and FunctionInstitute of ChemistryChinese Academy of SciencesBeijing100190 China University of Chinese Academy of Sciences Beijing100049 China

The asymmetric hydrogenation of N-heteroarenes provides an efficient method for the synthesis of optically active cyclic secondary *** this paper,we described an asymmetric hydrogenation of phenanthridines using a chiral mono-alkene-derived borane.A variety of dihydrophenanthridines were furnished in high yields with up to 93%*** current catalytic system was very sensitive for the steric hindrance of *** substituents at one phenyl group of phenanthridines were required to obtain the high *** large substituents on the carbon of the C=N bonds would diminish the reactivity sharply.

关键词： Asymmetric catalysis Hydrogenation Nitrogen heterocycles Phenanthridines Frustrated Lewis pairs Chiral boranes

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Dynamic Sulfur-Rich Polymers from Elemental Sulfur and Epoxides

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Chinese Journal of Polymer Science 2024年第10期42卷 1479-1487页

作者： Ke-Xiang Chen Chen-Hui cui Zhen Li Ting Xu Hao-Qing Teng zhi-Yuan He Yin-Zhou Guo Xiao-Qing Ming zhi-Shen Ge Yan-feng Zhang Tie-Jun Wang School of Chemistry Engineering Research Center of Energy Storage Materials and Devices Ministry of Education Xi'an Jiaotong University State Key Lab for Strength and Vibration of Mechanical Structures Department of Engineering Mechanics Xi'an Jiaotong University

Sulfur-containing dynamic polymers had attracted significant attention due to their unique chemical structures with high *** sulfur, an inexpensive industrial waste product, to synthesize dynamic polysulfide polymers through reverse vulcanization has been a notable approach. However, this method required high temperatures and resulted in the release of unpleasant oders. In this study, we presented a robust method for the preparation of sulfur-rich polymers with dynamic polysulfide bonds from elemental sulfur and inexpensive epoxide monomers via a one-pot strategy at the mild room temperature. Different types of polysulfide molecules and polymers were synthesized by reacting various epoxide compounds with sulfur, along with the investigation of their structures and dynamic behaviors. It was noteworthy that the obatined polymers prepared from m-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline and elemental sulfur exhibit multiple dynamic behaviors, including polysulfide metathesis and polysulfide-thiol exchange, enabling their rapid stress relaxation, self-healing, reprocessing and degradable properties of the cross-linked polymer. More importantly, the hydroxyl groups at the side chains from epoxide ring opening exhibited potential transesterification. This work provided a facile strategy for designing dynamic sulfur-rich polymers via a mild synthesis route.

关键词： Dynamic covalent bond Dynamic polymer Elemental sulfur Sulfur-containing polymer

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