To achieve a new type of carbon-based quantum dots with unique photoluminescence PL a simple approach for fabrication of graphene quantum dots GQDs with oxygen-rich groups was developed via the hydrothermal reaction b...To achieve a new type of carbon-based quantum dots with unique photoluminescence PL a simple approach for fabrication of graphene quantum dots GQDs with oxygen-rich groups was developed via the hydrothermal reaction by using graphene oxides GOs as a precursor. Transmission electron microscope TEM and atomic force microscope AFM characterizations confirmed that the sizes and heights of GQDs were 5.02±0.92 nm and 0.6 nm respectively.A strong PL emission exhibited unique excitation wavelength dependent features.Also the carbene-like free zigzag edge sites were proposed to be the origin of the strong PL emission.The GQDs were demonstrated to be a superior probe for Fe3+ detection in aqueous solution with a high sensitivity and feasibility due to the special coordinate interaction between Fe3+and the phenolic hydroxyl group at GQDs.展开更多
The growth and thermal stability of Au clusters on a partially-reduced rutile TiO2 (110)-1 × 1 surface were investigated by high-resolution photoelectron spectroscopy using synchrotron- radiation-light. The val...The growth and thermal stability of Au clusters on a partially-reduced rutile TiO2 (110)-1 × 1 surface were investigated by high-resolution photoelectron spectroscopy using synchrotron- radiation-light. The valence-band photoelectron spectroscopy results demonstrate that the Ti^3+3d feature attenuates quickly with the initial deposition of Au clusters, implying that Au clusters nucleate at the oxygen vacancy sites. The Au4f core-level photoelectron spectroscopy results directly prove the existence of charge transfer from oxygen vacancies to Au clusters. The thermal stability of Au clusters on the partially-reduced and stoichiometric TiO2(110) surfaces was also comparatively investigated by the annealing experiments. With the same film thickness, Au clusters are more thermally stable on the partially-reduced TiO2(110) surface than on the stoichiometric TiO2(110) surface. Meanwhile, large Au nanoparticles are more thermally stable than fine Au nanoparticles.展开更多
We describe a collinear velocity-map photoelectron imaging spectrometer, which combines a Wiley-McLaren time-of-flight mass analyzer with a dual-valve laser vaporization source for investigating size-selected cluster ...We describe a collinear velocity-map photoelectron imaging spectrometer, which combines a Wiley-McLaren time-of-flight mass analyzer with a dual-valve laser vaporization source for investigating size-selected cluster and reaction intermediate anions. To generate the reaction anions conveniently, two pulsed valves and a reaction channel are employed instead of premixing carrier gas. The collinear photoelectron imaging spectrometer adopts modified velocity-map electrostatic lens, and provides kinetic energy resolution better than 3%. The performance of the instrument is demonstrated on the photodetachment of Si4^- at 532 and 355 nm, and SiaC^- at 532 nm, respectively. In both cases, photoelectron spectra and anisotropy parameters are obtained from the images. For Si4^-, the spectra show two well- resolved vibrational progressions which correspond to the ground state and the first excited state of the neutral Si4 with peak spacing of 330 and 312 cm^-1, respectively. Preliminary results suggest that the apparatus is a powerful tool for characterizing the electronic structure and photodetachment dynamics of cluster anions.展开更多
The allyl radical has been observed in a low-pressure premixed gasoline/oxygen/argon flame by using tunable vacuum ultraviolet photoionization mass spectrometry, The ionization potential of the allyl radical is derive...The allyl radical has been observed in a low-pressure premixed gasoline/oxygen/argon flame by using tunable vacuum ultraviolet photoionization mass spectrometry, The ionization potential of the allyl radical is derived to be (8.13 ±0.02) eV from photoionization efficiency curve, In addition, a high level ab initzo Gaussian-3 (G3) method was used to calculate the energies of tile radical and its cation. The calculated adiabatic ionization potential is 8.18 eV, which is in excellent agreement with the experimental value. The result is helpful for identifying the allyl radical formed from other flames and for understanding the mechanism of soot formation.展开更多
Oxygen-poor vanadium oxide clusters, V2On+ (n=l, 2), V3On+ (n=l, 2, 3), and V4O3+, were produced by laser vaporization and were mass-selected and photodissociated with 532 and 266 nm photons. The geometric stru...Oxygen-poor vanadium oxide clusters, V2On+ (n=l, 2), V3On+ (n=l, 2, 3), and V4O3+, were produced by laser vaporization and were mass-selected and photodissociated with 532 and 266 nm photons. The geometric structures and possible dissociation channels of these clusters were determined based on the comparison of density functional calculations and pho- todissociation experiments. The experiments show that the dissociation of V2O+, V2O2+, and V3O3+ mainly occurs by loss of VO, while the dissociation of V3O+ and V4O3+ mainly occurs by loss of V atom. For the dissociation of V3O2+, the VO loss channel is slightly dominant compared to the V loss channel. The combination of experimental results and theoretical calculations suggests that the V loss channels of V3O+ and V4O3+ are single photon processes at both 532 and 266 nm. The VO loss channels of V2O2+ and V3O3+ are multiple-photon processes at both 532 and 266 nm.展开更多
Prediction of vapor-liquid equilibrium (VLE) is extremely necessary to separate liquid mixture in chemical production, especially when the required experimental data are difficult to measure, or the measurement is n...Prediction of vapor-liquid equilibrium (VLE) is extremely necessary to separate liquid mixture in chemical production, especially when the required experimental data are difficult to measure, or the measurement is not economical. The infinite dilution activities can be used to predict VLE. However, it needs both the ends of the activities that are difficult to obtain for many systems. In the present study, a new model is proposed for correlating the frequency shift of C-H stretching band of IR spectra over the whole concentration. Investigated mixtures in- clude water/2-propanol, water/N, N-dimethylformamide (DMF), water/methanol, water/ethanol, water/1, 4-dioxane, and water/dimethylsulfoxide (DMSO) systems. Simultaneous correlations of C--H frequency shift and VLE data are made. Furthermore, the VLE data were predicted with satisfactory results by the parameters obtained from IR spectra coupled with one ot the intinite chlution activity coefficients.展开更多
This paper introduces a new concept of community-based ecotourism (CBET) that originated in foreign countries. Then it analyzes the significance of CBET development in nature reserve (NR). The authors think that commu...This paper introduces a new concept of community-based ecotourism (CBET) that originated in foreign countries. Then it analyzes the significance of CBET development in nature reserve (NR). The authors think that community participation is the evitable choice of nature reserve′s conservation and development. CBET, as the self-improved model of ecotourism, can promote tourism community sustainable development. Based on the stakeholder analysis of CBET in NRs, this paper addresses the reality, especially the problem of CBET development in NRs of China. In order to develop CBET in NRs of China, this paper takes some suggestions to promote the community participation: 1)gradual political empowerment, 2) deep level economic incentive, 3) widespread educational support, 4) impartial distribution of community benefits, and 5) stakeholders cooperation.展开更多
Spectroscopic characterization of clusters is crucial to understanding the structures and reaction mechanisms at the microscopic level,but it has been proven to be a grand challenge for neutral clusters because the ab...Spectroscopic characterization of clusters is crucial to understanding the structures and reaction mechanisms at the microscopic level,but it has been proven to be a grand challenge for neutral clusters because the absence of a charge makes it di伍cult for the size selection and detection.Infrared(IR)spectroscopy based on threshold photoionization using a tunable vacuum ultraviolet free electron laser(VUV-FEL)has recently been developed in the lab.The IR-VUV depletion and IR+VUV enhancement spectroscopic techniques open new avenues for size-selected IR spectroscopies of a large variety of neutral clusters without confinement(i.e.,an ultraviolet chromophore,a messenger tag,or a host matrix).The spectroscopic principles have been demonstrated by investigations of some neutral water clusters and some metal carbonyls.Here,the spectroscopic principles and their applications for neutral clusters are reviewed.展开更多
In recent experiments [e.g., Nature Physics 2 (2006) 332], the enhanced light deflection in an atomic ensemble due to inhomogeneous fields is demonstrated by the electromagneticaJly induced transparency (EIT) base...In recent experiments [e.g., Nature Physics 2 (2006) 332], the enhanced light deflection in an atomic ensemble due to inhomogeneous fields is demonstrated by the electromagneticaJly induced transparency (EIT) based mechanism. In this paper, we explore a different mechanism for the similar phenomenon of the enhanced light deflection. This mechanism is based on the coherent population oscillation, which leads to the hole burning in the absorption spectrum. The medium causing the deflection of probe light is an ensemble of two-level atoms manipulated by a strong controlled field on the two photon resonances. In the large detuning condition, the response of the medium to the pump field and signal field is obtained with steady state approximation. And it is found that after the probe field travels across the medium, the signal ray bends due to the spatial-dependent profile of the control beam.展开更多
Infrared-vacuum ultraviolet (IR-VUV) spectra of neutral trimethylamine dimer were mea- sured in the 2500-3800 cm-1 region. Quantum chemical calculations were performed to identify the structure of the low-lying isom...Infrared-vacuum ultraviolet (IR-VUV) spectra of neutral trimethylamine dimer were mea- sured in the 2500-3800 cm-1 region. Quantum chemical calculations were performed to identify the structure of the low-lying isomers and to assign the observed spectral features. The bands at 2975 and 2949 cm-1 were assigned to the antisymmetric C-H stretching and the band at 2823 cm-1 to the symmetric C-H stretching, respectively. The 2739 cm-1 band was due to the CH3 bending overtone, which disappeared at low IR laser power of 1 mJ/mm2. The extra band at 2773 cm-1 could be due to Fermi resonance behavior of the light isotopologue, these are often close in energy and can strongly mix through cubic terms in the potential function. Experimental and theoretical results indicate the likely coexistence of multiple structures. The peak widths of IR spectra of neutral trimethylamine dimer are not significantly affected by the structural transformation, allowing the stretching modes to be well resolved.展开更多
Transition metal carbides have been shown to exhibit good catalytic performance that depends on their compositions and morphologies,and understanding such catalytic properties requires knowledge of their precise geome...Transition metal carbides have been shown to exhibit good catalytic performance that depends on their compositions and morphologies,and understanding such catalytic properties requires knowledge of their precise geometry,determination of which is challenging,particularly for clusters formed by multiple elements.In this study,we investigate the geometries and electronic structures of binary V_(n)C_(3)-(n=1-6)clusters and their neutrals using photoelectron spectroscopy and theoretical calculations based on density functional theory.The adiabatic detachment energies of V_(n)C_(3)-,or equally,the electron affinities of V_(n)C_(3),have been determined from the measured photoelectron spectra.Theoretical calculations reveal that the carbon atoms become separate when the number of V atoms increases in the clusters,i.e.,the C-C interactions present in small clusters are replaced by V-C and/or V-V interactions in larger ones.We further explore the composition dependent formation of cubic or cube-like structures in 8-atom VnCm(n+m=8)clusters.展开更多
A series of photochromic diarylethene derivatives containing different fluorophores was synthesized by the Sonogashira coupling reaction and characterized by 1H nuclear magnetic resonance (NMR), 13C NMR and mass spect...A series of photochromic diarylethene derivatives containing different fluorophores was synthesized by the Sonogashira coupling reaction and characterized by 1H nuclear magnetic resonance (NMR), 13C NMR and mass spectroscopy. Photochromic conversion of Cz-MS was observed and its structural change was confirmed by proton NMR. Switchable absorption and emission phenomena were observed for these molecules. These phenomena were attributed to the reversible photochromic fluorescence resonance energy transfer (pcFRET) process. The design of this novel photochromic system of Py-4MS enables information to be processed in a non-destructive manner. This overcomes the problem of the destructive nature of tracking photochromism using ultraviolet (UV)-vis spectroscopy.展开更多
With the frame of the time-dependent local density approximation, an efficient description of the optical response of clusters has been used to study the photo-absorption cross section of Na2 and Na4 clusters. It is s...With the frame of the time-dependent local density approximation, an efficient description of the optical response of clusters has been used to study the photo-absorption cross section of Na2 and Na4 clusters. It is shown that our calculated results are in good agreement with the experiment. In addition, our calculated spectrum for the Na4 cluster is in better agreement with experiment than the GW absorption spectrum.展开更多
The industrial silica fume pretreated by nitric acid at 80 °C was re-used in this work. Then, the obtained silica nanoparticles were surface functionalized by silane coupling agents, such as(3-Mercaptopropyl) tri...The industrial silica fume pretreated by nitric acid at 80 °C was re-used in this work. Then, the obtained silica nanoparticles were surface functionalized by silane coupling agents, such as(3-Mercaptopropyl) triethoxysilane(MPTES) and(3-Amincpropyl) trithoxysilane(APTES). Some further modifications were studied by chloroaceetyl choride and 1,8-Diaminoaphalene for amino modified silica. The surface functionalized silica nanoparticles were characterized by Fourier transform infrared(FI-IR) and X-ray photoelectron spectroscopy(XPS). The prepared adsorbent of surface functionalized silica nanoparticles with differential function groups were investigated in the selective adsorption about Pb2+, Cu2+, Hg2+, Cd2+ and Zn2+ions in aqueous solutions. The results show that the(3-Mercaptopropyl) triethoxysilane functionalized silica nanoparticles(SiO2-MPTES) play an important role in the selective adsorption of Cu2+ and Hg2+, the(3-Amincpropyl) trithoxysilane(APTES) functionalized silica nanoparticles(SiO2-APTES) exhibited maximum removal efficiency towards Pb2+ and Hg2+, the 1,8-Diaminoaphalene functionalized silica nanoparticles was excellent for removal of Hg2+ at room temperature, respectively.展开更多
A novel second-order nonlinear optical chromophore (DCDHF-2-V) was synthesized from 3-Hydroxy-3-methyl-2-butanae, propanedinitrile and 4-diethylaminobenzaldehyde by aldol condensation reaction. Molecular structural ...A novel second-order nonlinear optical chromophore (DCDHF-2-V) was synthesized from 3-Hydroxy-3-methyl-2-butanae, propanedinitrile and 4-diethylaminobenzaldehyde by aldol condensation reaction. Molecular structural characterization was investigated by elemental analysis, FTIR, and 1H-NMR spectra. The melting point obtained from DSC thermogram was almost 251 ℃, and the compound shows a thermal stability up to 270 ℃. Second-order NLO properties of the chromophore were measured by solvatochromic method. From the quantum-mechanical two-level model, it can be obtained that the μgβ value of DCDHF-2-V is 6520×10^-48esu atthe wavelength of 1064 nm.展开更多
Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, an...Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, and halide) radicals initiated by visible light can undergo radical addition to a carbon-carbon triple bond. Upon further transformation, the desired difunctionalized products are obtained. Some organometallic complexes can be activated by visible light;the difunctionalization of alkynes is catalyzed by these species. Other reagents like 1,3-dipole precursors could also react with alkynes to give difunctionalization products;here, the 1,3-dipole derivatives are obtained by visible light photocatalysis. So far, the strategy has been succeeded in the formation of C–C bonds and C–X bonds. Several valuable chemical skeletons have been constructed under mild conditions. However, high regio-and stereoselectivities in some direct difunctionalization methodologies are yet to be achieved.展开更多
Gold(I) thiolate compounds (i.e. AuLSR) are important precursors for the synthesis of atom- ically precise Aun(SR)m nanoclusters. However, the nature of the AuI-SR precursor remains elusive. Here, we report that...Gold(I) thiolate compounds (i.e. AuLSR) are important precursors for the synthesis of atom- ically precise Aun(SR)m nanoclusters. However, the nature of the AuI-SR precursor remains elusive. Here, we report that the Aul0(TBBT)10 complex is a universal precursor for the synthesis of Aun(TBBT)m nanoclusters (where TBBT 4-tertbutylbenzenethiol/thiolate). Interestingly, the Aul0(TBBT)10 complex is also found to be re-generated through extended etching of the Aun(SR)m nanoclusters with excess of TBBT thiol and O2. The formation of well-defined Aul0(TBBT)10 complex, instead of polymeric AuKSR, is attributed to the bulkiness of the TBBT thiol. Through 1D and 2D NMR charcteriztions, the structure of Aul0(TBBT)10 is correlated with the previously reported X-ray structure, which contains two inter-penetrated Aus(TBBT)5 rings. The photophysical property of Au10(TBBT)10 complex is further probed by femtosecond transient absorption spectroscopy. The acces- sibility of the precise Au10(TBBT)10 precursor improves the efficiency of the synthesis of the Aun(TBBT)m nanoclusters and is expected to further facilitate excellent control and understanding of the reaction mechanisms of nanocluster synthesis.展开更多
基金The National Basic Research Program of China(973Program)(No.2013CB932902)the National Natural Science Foundation of China(No.21201034,21173042)the Fundamental Research Funds for the Central Universities(No.3207044403)
文摘To achieve a new type of carbon-based quantum dots with unique photoluminescence PL a simple approach for fabrication of graphene quantum dots GQDs with oxygen-rich groups was developed via the hydrothermal reaction by using graphene oxides GOs as a precursor. Transmission electron microscope TEM and atomic force microscope AFM characterizations confirmed that the sizes and heights of GQDs were 5.02±0.92 nm and 0.6 nm respectively.A strong PL emission exhibited unique excitation wavelength dependent features.Also the carbene-like free zigzag edge sites were proposed to be the origin of the strong PL emission.The GQDs were demonstrated to be a superior probe for Fe3+ detection in aqueous solution with a high sensitivity and feasibility due to the special coordinate interaction between Fe3+and the phenolic hydroxyl group at GQDs.
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (No.20773113 and No.20803072), the Hundred Talent Program of Chinese Academy of Sciences, the MOE Program for Changjiang Scholars and Innovative Research Team (No.IRT0756), and the MPG-CAS Partner-group Program.
文摘The growth and thermal stability of Au clusters on a partially-reduced rutile TiO2 (110)-1 × 1 surface were investigated by high-resolution photoelectron spectroscopy using synchrotron- radiation-light. The valence-band photoelectron spectroscopy results demonstrate that the Ti^3+3d feature attenuates quickly with the initial deposition of Au clusters, implying that Au clusters nucleate at the oxygen vacancy sites. The Au4f core-level photoelectron spectroscopy results directly prove the existence of charge transfer from oxygen vacancies to Au clusters. The thermal stability of Au clusters on the partially-reduced and stoichiometric TiO2(110) surfaces was also comparatively investigated by the annealing experiments. With the same film thickness, Au clusters are more thermally stable on the partially-reduced TiO2(110) surface than on the stoichiometric TiO2(110) surface. Meanwhile, large Au nanoparticles are more thermally stable than fine Au nanoparticles.
基金ACKNOWLEDGMENTS We thank Professor Hai-yang Li for simulation electron trajectory, and H. Reisler for providing the image analysis software. This work was supported by the National Natural Science Foundation of China (No.20773126), the Ministry of Science and Technology of China, and the Chinese Academy of Sciences.
文摘We describe a collinear velocity-map photoelectron imaging spectrometer, which combines a Wiley-McLaren time-of-flight mass analyzer with a dual-valve laser vaporization source for investigating size-selected cluster and reaction intermediate anions. To generate the reaction anions conveniently, two pulsed valves and a reaction channel are employed instead of premixing carrier gas. The collinear photoelectron imaging spectrometer adopts modified velocity-map electrostatic lens, and provides kinetic energy resolution better than 3%. The performance of the instrument is demonstrated on the photodetachment of Si4^- at 532 and 355 nm, and SiaC^- at 532 nm, respectively. In both cases, photoelectron spectra and anisotropy parameters are obtained from the images. For Si4^-, the spectra show two well- resolved vibrational progressions which correspond to the ground state and the first excited state of the neutral Si4 with peak spacing of 330 and 312 cm^-1, respectively. Preliminary results suggest that the apparatus is a powerful tool for characterizing the electronic structure and photodetachment dynamics of cluster anions.
基金This work Was supported by the Knowledge Innovation funding of CAS and the Natural Science Foundation of China(NSFC No.20473081).
文摘The allyl radical has been observed in a low-pressure premixed gasoline/oxygen/argon flame by using tunable vacuum ultraviolet photoionization mass spectrometry, The ionization potential of the allyl radical is derived to be (8.13 ±0.02) eV from photoionization efficiency curve, In addition, a high level ab initzo Gaussian-3 (G3) method was used to calculate the energies of tile radical and its cation. The calculated adiabatic ionization potential is 8.18 eV, which is in excellent agreement with the experimental value. The result is helpful for identifying the allyl radical formed from other flames and for understanding the mechanism of soot formation.
基金This work was supported by the National Natural Science Foundation of China (No.20933008). The theoretical calculations were conducted on the ScGrid and Deepcomp7000 of the Supercomputing Center, Com- puter Network Information Center of Chinese Academy of Sciences. We thank Dr. Xun-lei Ding and Dr. Yan-xia Zhao for valuable discussion.
文摘Oxygen-poor vanadium oxide clusters, V2On+ (n=l, 2), V3On+ (n=l, 2, 3), and V4O3+, were produced by laser vaporization and were mass-selected and photodissociated with 532 and 266 nm photons. The geometric structures and possible dissociation channels of these clusters were determined based on the comparison of density functional calculations and pho- todissociation experiments. The experiments show that the dissociation of V2O+, V2O2+, and V3O3+ mainly occurs by loss of VO, while the dissociation of V3O+ and V4O3+ mainly occurs by loss of V atom. For the dissociation of V3O2+, the VO loss channel is slightly dominant compared to the V loss channel. The combination of experimental results and theoretical calculations suggests that the V loss channels of V3O+ and V4O3+ are single photon processes at both 532 and 266 nm. The VO loss channels of V2O2+ and V3O3+ are multiple-photon processes at both 532 and 266 nm.
基金Supported by the National Natural Science Foundation of China (No.20573093 and No.20434020).
文摘Prediction of vapor-liquid equilibrium (VLE) is extremely necessary to separate liquid mixture in chemical production, especially when the required experimental data are difficult to measure, or the measurement is not economical. The infinite dilution activities can be used to predict VLE. However, it needs both the ends of the activities that are difficult to obtain for many systems. In the present study, a new model is proposed for correlating the frequency shift of C-H stretching band of IR spectra over the whole concentration. Investigated mixtures in- clude water/2-propanol, water/N, N-dimethylformamide (DMF), water/methanol, water/ethanol, water/1, 4-dioxane, and water/dimethylsulfoxide (DMSO) systems. Simultaneous correlations of C--H frequency shift and VLE data are made. Furthermore, the VLE data were predicted with satisfactory results by the parameters obtained from IR spectra coupled with one ot the intinite chlution activity coefficients.
基金Under the auspices of the National Natural Science Foundation of China (No. 40371039)
文摘This paper introduces a new concept of community-based ecotourism (CBET) that originated in foreign countries. Then it analyzes the significance of CBET development in nature reserve (NR). The authors think that community participation is the evitable choice of nature reserve′s conservation and development. CBET, as the self-improved model of ecotourism, can promote tourism community sustainable development. Based on the stakeholder analysis of CBET in NRs, this paper addresses the reality, especially the problem of CBET development in NRs of China. In order to develop CBET in NRs of China, this paper takes some suggestions to promote the community participation: 1)gradual political empowerment, 2) deep level economic incentive, 3) widespread educational support, 4) impartial distribution of community benefits, and 5) stakeholders cooperation.
基金This work was supported by the National Natural Science Foundation of China(No.92061203 and No.21688102)the Strategic Priority Research Program of Chinese Academy of Sciences(XDB17000000)+3 种基金International Partnership Program of Chinese Academy of Sciences(121421KYSB20170012)Chinese Academy of Sciences(GJJSTD20190002)K.C.Wong Education Foundation(GJTD-2018-06)Dalian Institute of Chemical Physics(DICP DCLS201702).
文摘Spectroscopic characterization of clusters is crucial to understanding the structures and reaction mechanisms at the microscopic level,but it has been proven to be a grand challenge for neutral clusters because the absence of a charge makes it di伍cult for the size selection and detection.Infrared(IR)spectroscopy based on threshold photoionization using a tunable vacuum ultraviolet free electron laser(VUV-FEL)has recently been developed in the lab.The IR-VUV depletion and IR+VUV enhancement spectroscopic techniques open new avenues for size-selected IR spectroscopies of a large variety of neutral clusters without confinement(i.e.,an ultraviolet chromophore,a messenger tag,or a host matrix).The spectroscopic principles have been demonstrated by investigations of some neutral water clusters and some metal carbonyls.Here,the spectroscopic principles and their applications for neutral clusters are reviewed.
基金The project supported by the Natural Science Foundation of China under Grant Nos. 10775048, 10704023, 10775048, and 10325523the National Fundamental Research Program of China under Grant No. 2007CB925204the Scientific Research Fund of Hunan Provincial Education Department of China under Grant No. 07C579
文摘In recent experiments [e.g., Nature Physics 2 (2006) 332], the enhanced light deflection in an atomic ensemble due to inhomogeneous fields is demonstrated by the electromagneticaJly induced transparency (EIT) based mechanism. In this paper, we explore a different mechanism for the similar phenomenon of the enhanced light deflection. This mechanism is based on the coherent population oscillation, which leads to the hole burning in the absorption spectrum. The medium causing the deflection of probe light is an ensemble of two-level atoms manipulated by a strong controlled field on the two photon resonances. In the large detuning condition, the response of the medium to the pump field and signal field is obtained with steady state approximation. And it is found that after the probe field travels across the medium, the signal ray bends due to the spatial-dependent profile of the control beam.
文摘Infrared-vacuum ultraviolet (IR-VUV) spectra of neutral trimethylamine dimer were mea- sured in the 2500-3800 cm-1 region. Quantum chemical calculations were performed to identify the structure of the low-lying isomers and to assign the observed spectral features. The bands at 2975 and 2949 cm-1 were assigned to the antisymmetric C-H stretching and the band at 2823 cm-1 to the symmetric C-H stretching, respectively. The 2739 cm-1 band was due to the CH3 bending overtone, which disappeared at low IR laser power of 1 mJ/mm2. The extra band at 2773 cm-1 could be due to Fermi resonance behavior of the light isotopologue, these are often close in energy and can strongly mix through cubic terms in the potential function. Experimental and theoretical results indicate the likely coexistence of multiple structures. The peak widths of IR spectra of neutral trimethylamine dimer are not significantly affected by the structural transformation, allowing the stretching modes to be well resolved.
基金the Doctoral Start-up Funding of Zhengzhou University of Light Industry(No.2017BSJJ030)Henan Province Science Fund for Excellent Young Scholars(No.202300410494)+4 种基金the Beijing Municipal Science and Technology Commission(No.Z191100007219009)for supportsthe VSC(Flemish Supercomputer Center),funded by the Research Foundation-Flanders(FWO)the Flemish Government-department EWIthe support of Xi’an Jiaotong University via the“Young Talent Support Plan”the“Fundamental Research Funds for Central Universities”。
文摘Transition metal carbides have been shown to exhibit good catalytic performance that depends on their compositions and morphologies,and understanding such catalytic properties requires knowledge of their precise geometry,determination of which is challenging,particularly for clusters formed by multiple elements.In this study,we investigate the geometries and electronic structures of binary V_(n)C_(3)-(n=1-6)clusters and their neutrals using photoelectron spectroscopy and theoretical calculations based on density functional theory.The adiabatic detachment energies of V_(n)C_(3)-,or equally,the electron affinities of V_(n)C_(3),have been determined from the measured photoelectron spectra.Theoretical calculations reveal that the carbon atoms become separate when the number of V atoms increases in the clusters,i.e.,the C-C interactions present in small clusters are replaced by V-C and/or V-V interactions in larger ones.We further explore the composition dependent formation of cubic or cube-like structures in 8-atom VnCm(n+m=8)clusters.
基金Project supported by the National Natural Science Foundation of China (No. 20674070)the Natural Science Foundation of Zhejiang Province (No. R404109), China
文摘A series of photochromic diarylethene derivatives containing different fluorophores was synthesized by the Sonogashira coupling reaction and characterized by 1H nuclear magnetic resonance (NMR), 13C NMR and mass spectroscopy. Photochromic conversion of Cz-MS was observed and its structural change was confirmed by proton NMR. Switchable absorption and emission phenomena were observed for these molecules. These phenomena were attributed to the reversible photochromic fluorescence resonance energy transfer (pcFRET) process. The design of this novel photochromic system of Py-4MS enables information to be processed in a non-destructive manner. This overcomes the problem of the destructive nature of tracking photochromism using ultraviolet (UV)-vis spectroscopy.
基金The project supported by National Natural Science Foundation of China under Grant Nos. 10405025, 10575012, 10435020, and 10535010
文摘With the frame of the time-dependent local density approximation, an efficient description of the optical response of clusters has been used to study the photo-absorption cross section of Na2 and Na4 clusters. It is shown that our calculated results are in good agreement with the experiment. In addition, our calculated spectrum for the Na4 cluster is in better agreement with experiment than the GW absorption spectrum.
基金Project(2012CB722803)supported by the Key Project of National Basic Research and Development Program of ChinaProject(U1202271)supported by the National Natural Science Foundation of ChinaProject(IRT1250)supported by the Program for Innovative Research Team in University of Ministry of Education of China
文摘The industrial silica fume pretreated by nitric acid at 80 °C was re-used in this work. Then, the obtained silica nanoparticles were surface functionalized by silane coupling agents, such as(3-Mercaptopropyl) triethoxysilane(MPTES) and(3-Amincpropyl) trithoxysilane(APTES). Some further modifications were studied by chloroaceetyl choride and 1,8-Diaminoaphalene for amino modified silica. The surface functionalized silica nanoparticles were characterized by Fourier transform infrared(FI-IR) and X-ray photoelectron spectroscopy(XPS). The prepared adsorbent of surface functionalized silica nanoparticles with differential function groups were investigated in the selective adsorption about Pb2+, Cu2+, Hg2+, Cd2+ and Zn2+ions in aqueous solutions. The results show that the(3-Mercaptopropyl) triethoxysilane functionalized silica nanoparticles(SiO2-MPTES) play an important role in the selective adsorption of Cu2+ and Hg2+, the(3-Amincpropyl) trithoxysilane(APTES) functionalized silica nanoparticles(SiO2-APTES) exhibited maximum removal efficiency towards Pb2+ and Hg2+, the 1,8-Diaminoaphalene functionalized silica nanoparticles was excellent for removal of Hg2+ at room temperature, respectively.
文摘A novel second-order nonlinear optical chromophore (DCDHF-2-V) was synthesized from 3-Hydroxy-3-methyl-2-butanae, propanedinitrile and 4-diethylaminobenzaldehyde by aldol condensation reaction. Molecular structural characterization was investigated by elemental analysis, FTIR, and 1H-NMR spectra. The melting point obtained from DSC thermogram was almost 251 ℃, and the compound shows a thermal stability up to 270 ℃. Second-order NLO properties of the chromophore were measured by solvatochromic method. From the quantum-mechanical two-level model, it can be obtained that the μgβ value of DCDHF-2-V is 6520×10^-48esu atthe wavelength of 1064 nm.
基金supported by Zhejiang Provincial Natural Science Foundation of China(LR19B020001)the National Natural Science Foundation of China(21472162,21772171)the National Basic Research Program of China(2015CB856600)~~
文摘Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, and halide) radicals initiated by visible light can undergo radical addition to a carbon-carbon triple bond. Upon further transformation, the desired difunctionalized products are obtained. Some organometallic complexes can be activated by visible light;the difunctionalization of alkynes is catalyzed by these species. Other reagents like 1,3-dipole precursors could also react with alkynes to give difunctionalization products;here, the 1,3-dipole derivatives are obtained by visible light photocatalysis. So far, the strategy has been succeeded in the formation of C–C bonds and C–X bonds. Several valuable chemical skeletons have been constructed under mild conditions. However, high regio-and stereoselectivities in some direct difunctionalization methodologies are yet to be achieved.
基金supported by the U.S.National Science Foundation(DMR-1808675)
文摘Gold(I) thiolate compounds (i.e. AuLSR) are important precursors for the synthesis of atom- ically precise Aun(SR)m nanoclusters. However, the nature of the AuI-SR precursor remains elusive. Here, we report that the Aul0(TBBT)10 complex is a universal precursor for the synthesis of Aun(TBBT)m nanoclusters (where TBBT 4-tertbutylbenzenethiol/thiolate). Interestingly, the Aul0(TBBT)10 complex is also found to be re-generated through extended etching of the Aun(SR)m nanoclusters with excess of TBBT thiol and O2. The formation of well-defined Aul0(TBBT)10 complex, instead of polymeric AuKSR, is attributed to the bulkiness of the TBBT thiol. Through 1D and 2D NMR charcteriztions, the structure of Aul0(TBBT)10 is correlated with the previously reported X-ray structure, which contains two inter-penetrated Aus(TBBT)5 rings. The photophysical property of Au10(TBBT)10 complex is further probed by femtosecond transient absorption spectroscopy. The acces- sibility of the precise Au10(TBBT)10 precursor improves the efficiency of the synthesis of the Aun(TBBT)m nanoclusters and is expected to further facilitate excellent control and understanding of the reaction mechanisms of nanocluster synthesis.