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
Pyrolysis of benzene at 30 Torr was studied from 1360 K to 1820 K in this work. Synchrotron vacuum ultraviolet photoionization mass spectrometry was employed to detect the pyroly- sis products such as radicals, isomer...Pyrolysis of benzene at 30 Torr was studied from 1360 K to 1820 K in this work. Synchrotron vacuum ultraviolet photoionization mass spectrometry was employed to detect the pyroly- sis products such as radicals, isomers and polycyclic aromatic hydrocarbons, and measure their mole fraction profiles versus temperature. A low-pressure pyrolysis model of benzene was developed and validated by the experimental results. Rate of production analysis was performed to reveal the major reaction networks in both fuel decomposition and aromatic growth processes. It is concluded that benzene is mainly decomposed via H-abstraction reaction to produce phenyl and partly decomposed via unimolecular decomposition reac- tions to produce propargyl or phenyl. The decomposition process stops at the formation of acetylene and polyyne species like diacetylene and 1,3,5-hexatriyne due to their high thermal stabilities. Besides, the aromatic growth process in the low-pressure pyrolysis of benzene is concluded to initiate from benzene and phenyl, and is controlled by the even carbon growth mechanism due to the inhibited formation of C5 and C7 species which play important roles in the odd carbon growth mechanism.展开更多
Vacuum ultraviolet (VUV) photoionization and dissociative photoionization of capecitabine and its metabolites, 51-deoxy-5-fiuorocytidine (5'-DFCR) and 51-deoxy-5- fiuorouridine (5'- DFUR), were investigated wi...Vacuum ultraviolet (VUV) photoionization and dissociative photoionization of capecitabine and its metabolites, 51-deoxy-5-fiuorocytidine (5'-DFCR) and 51-deoxy-5- fiuorouridine (5'- DFUR), were investigated with infrared laser desorption/tunable synchrotron VUV photoionization mass spectrometry. Molecular ions (M+) with small amounts of fragments can be found for these compounds at relatively low photon energies, while more fragment ions would be produced by increasing the photon energies. (M-H2O)+, (base+H)+, (base+2H)+, (base+30)+, (base+60)+, and sugar moiety were proposed for these nucleoside drugs with similar backbones. Decomposition channels for the major fragments were discussed in detail. Moreover, ab initio calculations were introduced to study the dehydration pathways of three fluoro-nucleosides. Corresponding appearance energies for the (M-H2O)+ ions were computed.展开更多
The pyrolysis of n-butane and i-butane at low pressure was investigated from 823-1823 K in an electrically heated flow reactor using synchrotron vacuum ultraviolet photoionization mass spectrometry. More than 20 speci...The pyrolysis of n-butane and i-butane at low pressure was investigated from 823-1823 K in an electrically heated flow reactor using synchrotron vacuum ultraviolet photoionization mass spectrometry. More than 20 species, especially several radicals and isomers, were detected and identified from the measurements of photoionization efficiency (PIE) spectra. Based on the mass spectrometric analysis, the characteristics of n-butane and i-butane pyrolysis were discussed, which provided experimental evidences for the discussion of decomposition pathways of butane isomers. It is concluded that the isomeric structures of n-butane and i-butane have strong influence on their main decomposition pathways, and lead to dramatic differences in their mass spectra and PIE spectra such as the different dominant products and isomeric structures of butene products. Furthermore, compared with n-butane,i-butane can produce strong signals of benzene at low temperature in its pyrolysis due to the enhanced formation of benzene precursors like propargyl and C4 species, which provides experimental clues to explain the higher sooting tendencies of iso-alkanes than n-alkanes.展开更多
Vacuum ultraviolet photon-induced ionization and dissociation of isoleucine are investi- gated with synchrotron radiation photoionization mass spectroscopy and theoretical cal- culations. The main fragment ions at m/z...Vacuum ultraviolet photon-induced ionization and dissociation of isoleucine are investi- gated with synchrotron radiation photoionization mass spectroscopy and theoretical cal- culations. The main fragment ions at m/z=86, 75, 74, 69, 57, 46, 45, 44, 41, 30, 28, and 18 from isoleucine are observed in the mass spectrum at the photon energy of 13 eV. From the photoionization efficiency curves, appearance energies for the principal fragment ions CsH12N+ (rn/z=86), C2H5NO2+ (m/z=75), C5H9+ (rn/z=-69), C4H9+ (m/z=57), and CH4N+ (m/z=30) are determined to be 8.844-0.07, 9.254-0.06, 10.20-4-0.12, 9.254-0.10, and 11.05+0.07 eV, respectively, and possible formation pathways are established in detail by the calculations at the B3LYP/6-31++G(d, p) levels. These proposed channels include simple bond cleavage reactions as well as reactions involving intermediates and transition structures. The experimental and computational appearance energies or barriers are in good agreement.展开更多
We have prepared and characterized atomically well-defined model systems for ceria-supported Pt-Co core-shell catalysts. Pt@Co and Co@Pt core-shell nanostructures were grown on well-ordered CeO2(111) films on Cu(111) ...We have prepared and characterized atomically well-defined model systems for ceria-supported Pt-Co core-shell catalysts. Pt@Co and Co@Pt core-shell nanostructures were grown on well-ordered CeO2(111) films on Cu(111) by physical vapour deposition of Pt and Co metals in ultrahigh vacuum and investigated by means of synchrotron radiation photoelectron spectroscopy and resonant photoemission spectroscopy. The deposition of Co onto CeO2(111) yields CoCeO2(111) solid solution at low Co coverage(0.5 ML), followed by the growth of metallic Co nanoparticles at higher Co coverages. Both Pt@Co and Co@Pt model structures are stable against sintering in the temperature range between 300 and 500 K. After annealing at 500 K, the Pt@Co nanostructure contains nearly pure Co-shell while the Pt-shell in the Co@Pt is partially covered by metallic Co. Above 550 K, the re-ordering in the near surface regions yields a subsurface Pt-Co alloy and Pt-rich shells in both Pt@Co and Co@Pt nanostructures. In the case of Co@Pt nanoparticles, the chemical ordering in the near surface region depends on the initial thickness of the deposited Pt-shell. Annealing of the Co@Pt nanostructures in the presence of O2 triggers the decomposition of Pt-Co alloy along with the oxidation of Co, regardless of the thickness of the initial Pt-shell. Progressive oxidation of Co coupled with adsorbate-induced Co segregation leads to the formation of thick CoO layers on the surfaces of the supported Co@Pt nanostructures. This process is accompanied by the disintegration of the CeO2(111) film and encapsulation of oxidized Co@Pt nanostructures by CeO2 upon annealing in O2 above 550 K. Notably, during oxidation and reduction cycles with O2 and H2 at different temperatures, the changes in the structure and chemical composition of supported Co@Pt nanostructures were driven mainly by oxidation while reduction treatments had little effect regardless of the initial thickness of the Pt-shell.展开更多
The pyrolysis of pyridine (5.26% pyridine in argon) was performed with tunable synchrotron vacuum ultraviolet photoionization and molecular-beam mass spectrometry technique at the temperature range of 1255-1765 K at...The pyrolysis of pyridine (5.26% pyridine in argon) was performed with tunable synchrotron vacuum ultraviolet photoionization and molecular-beam mass spectrometry technique at the temperature range of 1255-1765 K at 267 Pa. About 20 products and intermediates, containing major species H2, HCN, C2H2, C5H3N, C4H2, and C3H3N, were identified by near-threshold measurements of photoionization mass spectra and their mole fractions vs. temperatures were estimated. The major reaction pathways are analyzed based on the experimental observations.展开更多
Vacuum ultraviolet(VUV)photoionization and photodissociation of methylcyclohexane have been studied utilizing a reflectron time-of-flight mass spectrometer(RTOF-MS)with synchrotron radiation source.Photoionization eff...Vacuum ultraviolet(VUV)photoionization and photodissociation of methylcyclohexane have been studied utilizing a reflectron time-of-flight mass spectrometer(RTOF-MS)with synchrotron radiation source.Photoionization efficiency curves(PIEs)of molecule ion C7H14^+ and fragment ions C7H13^+,C6H11^+,C6H10+,C5H10^+,C5H9^+,C4H8^+,C4H7^+,and C3H5^+ were observed.The ionization energy of methylcyclohexane was measured to be(9.80±0.03)eV,and appearance energies of fragment ions were determined from the PIEs.Optimized structures of transitional states,intermediates and product ions were characterized at the B3LYP/6-31G(d)level and the energies were calculated using G3B3 method.Formation channels of dominating fragment ions were proposed.Intramolecular hydrogen migrations and carbon ring-opening were the foremost processes in fragmentation pathways of methylcyclohexane.展开更多
The dissociative photoionization of cyclopentanone was investigated by means of a reflectron time-of-flight mass spectrometer(RTOF-MS)with tunable vacuum ultraviolet synchrotron radiation in the photon energy range of...The dissociative photoionization of cyclopentanone was investigated by means of a reflectron time-of-flight mass spectrometer(RTOF-MS)with tunable vacuum ultraviolet synchrotron radiation in the photon energy range of 9.0~15.5 eV.The photoionization efficiency(PIE)curves for molecular ion and fragment ions were measured.The ionization energy of cyclopentanone was determined to be 9.230.03 eV.Fragment ions from the dissociative photoionization of cyclopentanone were identified as C5H7O+,C4H5O+,C4H8+/C3H4O+,C3H3O+,C4H6+,C2H4O+,C3H6+,C3H5+,C3H4+,C3H3+,C2H5+and C2H4+.With the aid of the ab initio calculations at theωB97X-D/6-31+G(d,p)level of theory,the dissociative mechanisms of C5H8O+are proposed.Ring opening and hydrogen migrations are the predominant processes in most of the fragmentation pathways of cyclopentanone.展开更多
The photoionization and dissociation of 2-methyl-2-propen-1-ol(MPO)have been investigated by using molecular beam experimental apparatus with tunable vacuum ultraviolet synchrotron radiation in the photon energy regio...The photoionization and dissociation of 2-methyl-2-propen-1-ol(MPO)have been investigated by using molecular beam experimental apparatus with tunable vacuum ultraviolet synchrotron radiation in the photon energy region of 8.0-15.5 eV.The photoionization efficiency(PIE)curves for molecule ion and fragment ions:C4H8O^+,C4H7O^+,C3H5O^+,C4H7^+,C4H6^+,C4H5^+,C2H4O^+,C2H3O+,C3H6^+,C3H5^+,C3H3^+,CH3O^+,CHO^+have been measured,and the ionization energy(IE)and the appearance energies(AEs)of the fragment ions have been obtained.The stable species and the first order saddle points have been calculated on the CCSD(T)/cc-pvTZ//B3LYP/6-31+G(d,p)level.With combination of theoretical and experimental results,the dissociative photoionization pathways of 2-methyl-2-propen-1-ol are proposed.Hydrogen migrations within the molecule are the dominant processes in most of the fragmentation pathways of MPO.展开更多
A comprehensive experimental study of the premixed ethylene/oxygen/argon flame at 2.667 kPa with a stoichiometric equivalence ratio (Ф=1) was performed with the tunable synchrotron photoionization and molecular-bea...A comprehensive experimental study of the premixed ethylene/oxygen/argon flame at 2.667 kPa with a stoichiometric equivalence ratio (Ф=1) was performed with the tunable synchrotron photoionization and molecular-beam sampling mass spectrometry techniques. The isomers of most observed species in the flame were unambiguously identified by measurements of the photoionization etticiency spectra, e.g. C3H4, C2H4O and C4H4. The mole fraction profiles of species up to C7H8 were measured by scanning the burner position at the selected photon energies near ionization thresholds, and the flame temperature profile was obtained by using Pt/Pt-13%Rh thermocouple. Compared with the previous studies, a lot of new flame species: C3H2, C3H3, C3H5, C2H6O, C4H2, C4H4, C4H6, C3H4O, C3H6O, C3H8O, C5H6, C4H8O and C7H8, were observed. A series of free radicals in the flame are detected to be CH3, C2H3, C2H5, HCO, C3H3 and C3H5. Based on the experimental work, a reduced reaction mechanism was developed including 40 species and 223 reactions. Modeling and measurements agree well for the major species and most intermediates. A detailed kinetic model is desired for this flame.展开更多
Molecular frame photoemission is a very sensitive probe of the photoionization (PI) dynamics of molecules. This paper reports a comparative study of non-resonant and resonant photoionization of D2 induced by VUV cir...Molecular frame photoemission is a very sensitive probe of the photoionization (PI) dynamics of molecules. This paper reports a comparative study of non-resonant and resonant photoionization of D2 induced by VUV circularly polarized synchrotron radiation at SOLEIL at the level of the molecular frame photoelectron angular distributions (MFPADs). We use the vector correlation method which combines imaging and time-of-flight resolved electron-ion coincidence techniques, and a generalized formalism for the expression of the Ⅰ(χ, θe, Фe) MFPADs, where χ is the orientation of the molecular axis with respect to the light quantization axis and (θe, Фe) the electron emission direction in the molecular frame. Selected MFPADs for a molecule aligned parallel or perpendicular to linearly polarized light, or perpendicular to the propagation axis of circularly polarized light, are presented for dissociative photoionization (DPI) of D2 at two photon excitation energies, hv=19 eV, where direct PI is the only channel opened, and hv=32.5 eV, i.e. in the region involving resonant excitation of Q1 and Q2 doubly excited state series. We discuss in particular the properties of the circular dichroism characterizing photoemission in the molecular frame for direct and resonant PI. In the latter case, a remarkable behavior is observed which may be attributed to the interference occurring between undistinguishable autoionization decay channels.展开更多
A novel analysis approach using atomic fluorescence excited by synchrotron radiation is presented. A system for synchrotron radiation-atomic fluorescence spectrometry is developed, and experimental conditions such as ...A novel analysis approach using atomic fluorescence excited by synchrotron radiation is presented. A system for synchrotron radiation-atomic fluorescence spectrometry is developed, and experimental conditions such as flow rate, analyte acidity, concentration of pre-reducing and hydrogenation system are optimized. The proposed method is successfully applied to get an excitation spectrum of arsenic. Seven of ten primary spectral lines, four of which have never been reported by means of atomic fluorescence spectrometry, agree well with the existing reports. The other three are proposed for the first time. Excitation potentials and possible transitions are investigated. Especially for the prominent line at 234.99 nm, the mechanism of generation is discussed and a model of energy transition processes is proposed.展开更多
The authors synthesized very pure dimer phase of coroneae by simple heat-treatment and subsequent sublimation purification. It was confirmed by laser desorption/ionization mass spectroscopy measurements that pure dime...The authors synthesized very pure dimer phase of coroneae by simple heat-treatment and subsequent sublimation purification. It was confirmed by laser desorption/ionization mass spectroscopy measurements that pure dimer phase of coronenes can be obtained by controlling the fusing and sublimation temperatures. The crystal structure of the dimer phase was analyzed by synchrotron XRD (X-ray diffraction) experiments. It was also found that very bright red light is emitted by irradiating ultra violet light (λ = 350 nm) to the dimer phase. The external and internal quantum yields were determined to be 5.56% and 6.95%, respectively.展开更多
The NSLS-II (National Synchrotron Light Source II) is a state-of-the-art 3 GeV third generation light source currently under integrated testing and commissioning at Brook_haven National Laboratory. The vacuum system...The NSLS-II (National Synchrotron Light Source II) is a state-of-the-art 3 GeV third generation light source currently under integrated testing and commissioning at Brook_haven National Laboratory. The vacuum systems are monitored by vacuum gauges and ion pump current. The gate valves are controlled by PLC (programmable logic controllers) using voting scheme. EPICS (Experimental Physics and Industrial Control System) application codes provide the high level monitoring and control through the input-output controllers. This paper will discuss the commissioning status of the various aspects of vacuum control system.展开更多
The binding of (-)-epigallocatechin-3-O-gallate (EGCG) to bovine serum albumin (BSA) were investigated for the first time with spectral methods, including fluorescence and absorption spectrometry under simulativ...The binding of (-)-epigallocatechin-3-O-gallate (EGCG) to bovine serum albumin (BSA) were investigated for the first time with spectral methods, including fluorescence and absorption spectrometry under simulative physiological conditions. A strong fluorescence quenching reaction of EGCG to BSA was observed. It was proved that the fluorescence quenching of BSA by addition of EGCG was a result of the formation of EGCG-BSA complex. The binding constant K and the number of binding sites n were determined at physiological conditions and three different temperatures with fluorescence quenching method. The binding distance R and transfer efficiency E between BSA and EGCG were also obtained according to Forster theory of non-radiation energy transfer. The effects of Al^3+, Cu^2+, Mg^2+ and Fe^2+ on the binding constant between EGCG and BSA were studied at 298 K. The effect of EGCG on the conformation of BSA was also analyzed by synchronous fluorescence spectroscopy. PACS. 21. 10. Dr; 32. 50. +d; 32. 30. Jc; 82.80. Dx展开更多
The 3rd generation synchrotron light source requires high level of electron beam orbit stability.Shanghai Synchrotron Radiation Facility (SSRF) is a 3rd generation light source under construction;its orbit stability r...The 3rd generation synchrotron light source requires high level of electron beam orbit stability.Shanghai Synchrotron Radiation Facility (SSRF) is a 3rd generation light source under construction;its orbit stability requirement is up to micro or sub-micro range.The storage ring mechanical components vibration caused by the ground motion would influence the orbit stability.The ground motion of SSRF is severe.It is essential to control the vibration of the mechanical components.Vibration damping is an effective method to control the vibration.The author designed a vibration damping structure for the SSRF mechanical components.The test results show that it can effectively control the mechanical vibration.展开更多
In this paper,the slow orbit feedback system of HLS,including the feedback principle,the hardware,the software and the main operation results,is briefly introduced.With the help of slow orbit feedback system,the verti...In this paper,the slow orbit feedback system of HLS,including the feedback principle,the hardware,the software and the main operation results,is briefly introduced.With the help of slow orbit feedback system,the vertical orbit stability of HLS is better than 30 microns,which meets the requirement of synchrotron radiation users and is comparable with the international advanced level of orbit stability in the same kind of machines.展开更多
PSD yield is a key criterion to evaluate the vacuum chamber material and its surface pretreatment in an electron storage ring.In this paper,a stainless steel vacuum chamber of 1500 mm in diameter has been tested befor...PSD yield is a key criterion to evaluate the vacuum chamber material and its surface pretreatment in an electron storage ring.In this paper,a stainless steel vacuum chamber of 1500 mm in diameter has been tested before and after TiN film coating on PSD experiment station of Machine Study Beamline of NSRL.Test results show that TiN film coating is an effective method to reduce photon stimulated desorption for the stainless steel material.展开更多
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This work is supported by the National Natu- ral Science Foundation of China (No.51106146 and No.51036007), China Postdoctoral Science Foundation (No.20100480047 and No.201104326), Chinese Univer- sities Scientific Fund (No.WK2310000010), and Chinese Academy of Sciences.
文摘Pyrolysis of benzene at 30 Torr was studied from 1360 K to 1820 K in this work. Synchrotron vacuum ultraviolet photoionization mass spectrometry was employed to detect the pyroly- sis products such as radicals, isomers and polycyclic aromatic hydrocarbons, and measure their mole fraction profiles versus temperature. A low-pressure pyrolysis model of benzene was developed and validated by the experimental results. Rate of production analysis was performed to reveal the major reaction networks in both fuel decomposition and aromatic growth processes. It is concluded that benzene is mainly decomposed via H-abstraction reaction to produce phenyl and partly decomposed via unimolecular decomposition reac- tions to produce propargyl or phenyl. The decomposition process stops at the formation of acetylene and polyyne species like diacetylene and 1,3,5-hexatriyne due to their high thermal stabilities. Besides, the aromatic growth process in the low-pressure pyrolysis of benzene is concluded to initiate from benzene and phenyl, and is controlled by the even carbon growth mechanism due to the inhibited formation of C5 and C7 species which play important roles in the odd carbon growth mechanism.
文摘Vacuum ultraviolet (VUV) photoionization and dissociative photoionization of capecitabine and its metabolites, 51-deoxy-5-fiuorocytidine (5'-DFCR) and 51-deoxy-5- fiuorouridine (5'- DFUR), were investigated with infrared laser desorption/tunable synchrotron VUV photoionization mass spectrometry. Molecular ions (M+) with small amounts of fragments can be found for these compounds at relatively low photon energies, while more fragment ions would be produced by increasing the photon energies. (M-H2O)+, (base+H)+, (base+2H)+, (base+30)+, (base+60)+, and sugar moiety were proposed for these nucleoside drugs with similar backbones. Decomposition channels for the major fragments were discussed in detail. Moreover, ab initio calculations were introduced to study the dehydration pathways of three fluoro-nucleosides. Corresponding appearance energies for the (M-H2O)+ ions were computed.
基金This work is supported by the National. Natural Science Foundation of China (No.51106146, No.51036007, No.U1232127), the China Postdoctoral Science Foundation (No.20100480047 and No.201104326), the Chinese Universities Scientific Fund (No.WK2310000010), the Anhui Science & Technology Department (No.l1040606Q49), and the Chinese Academy of Sciences.
文摘The pyrolysis of n-butane and i-butane at low pressure was investigated from 823-1823 K in an electrically heated flow reactor using synchrotron vacuum ultraviolet photoionization mass spectrometry. More than 20 species, especially several radicals and isomers, were detected and identified from the measurements of photoionization efficiency (PIE) spectra. Based on the mass spectrometric analysis, the characteristics of n-butane and i-butane pyrolysis were discussed, which provided experimental evidences for the discussion of decomposition pathways of butane isomers. It is concluded that the isomeric structures of n-butane and i-butane have strong influence on their main decomposition pathways, and lead to dramatic differences in their mass spectra and PIE spectra such as the different dominant products and isomeric structures of butene products. Furthermore, compared with n-butane,i-butane can produce strong signals of benzene at low temperature in its pyrolysis due to the enhanced formation of benzene precursors like propargyl and C4 species, which provides experimental clues to explain the higher sooting tendencies of iso-alkanes than n-alkanes.
基金V. ACKNOWLEDGMENTS This work is supported by the National Natural Science Foundation of China (No.10875126 and No.10979048) and the Specialized Research Fund for the Doctoral Program of Higher Education, SRF for ROCS, SEM.
文摘Vacuum ultraviolet photon-induced ionization and dissociation of isoleucine are investi- gated with synchrotron radiation photoionization mass spectroscopy and theoretical cal- culations. The main fragment ions at m/z=86, 75, 74, 69, 57, 46, 45, 44, 41, 30, 28, and 18 from isoleucine are observed in the mass spectrum at the photon energy of 13 eV. From the photoionization efficiency curves, appearance energies for the principal fragment ions CsH12N+ (rn/z=86), C2H5NO2+ (m/z=75), C5H9+ (rn/z=-69), C4H9+ (m/z=57), and CH4N+ (m/z=30) are determined to be 8.844-0.07, 9.254-0.06, 10.20-4-0.12, 9.254-0.10, and 11.05+0.07 eV, respectively, and possible formation pathways are established in detail by the calculations at the B3LYP/6-31++G(d, p) levels. These proposed channels include simple bond cleavage reactions as well as reactions involving intermediates and transition structures. The experimental and computational appearance energies or barriers are in good agreement.
基金funded by the European Community(FP7-NMP.2012.1.1-1 project chip CAT,Reference No.310191)by the Deutsche Forschungsgemeinschaft(DFG)within the Excellence Cluster“Engineering of Advanced Materials”in the framework of the excellence initiative+2 种基金support by the DFG is acknowledged through the Priority Program SPP 1708 and the Research Unit FOR 1878supported by structural funds under project CZ.02.1.01/0.0/0.0/16_025/0007414by the Czech Ministry of Education(grant LM2015057)。
文摘We have prepared and characterized atomically well-defined model systems for ceria-supported Pt-Co core-shell catalysts. Pt@Co and Co@Pt core-shell nanostructures were grown on well-ordered CeO2(111) films on Cu(111) by physical vapour deposition of Pt and Co metals in ultrahigh vacuum and investigated by means of synchrotron radiation photoelectron spectroscopy and resonant photoemission spectroscopy. The deposition of Co onto CeO2(111) yields CoCeO2(111) solid solution at low Co coverage(0.5 ML), followed by the growth of metallic Co nanoparticles at higher Co coverages. Both Pt@Co and Co@Pt model structures are stable against sintering in the temperature range between 300 and 500 K. After annealing at 500 K, the Pt@Co nanostructure contains nearly pure Co-shell while the Pt-shell in the Co@Pt is partially covered by metallic Co. Above 550 K, the re-ordering in the near surface regions yields a subsurface Pt-Co alloy and Pt-rich shells in both Pt@Co and Co@Pt nanostructures. In the case of Co@Pt nanoparticles, the chemical ordering in the near surface region depends on the initial thickness of the deposited Pt-shell. Annealing of the Co@Pt nanostructures in the presence of O2 triggers the decomposition of Pt-Co alloy along with the oxidation of Co, regardless of the thickness of the initial Pt-shell. Progressive oxidation of Co coupled with adsorbate-induced Co segregation leads to the formation of thick CoO layers on the surfaces of the supported Co@Pt nanostructures. This process is accompanied by the disintegration of the CeO2(111) film and encapsulation of oxidized Co@Pt nanostructures by CeO2 upon annealing in O2 above 550 K. Notably, during oxidation and reduction cycles with O2 and H2 at different temperatures, the changes in the structure and chemical composition of supported Co@Pt nanostructures were driven mainly by oxidation while reduction treatments had little effect regardless of the initial thickness of the Pt-shell.
基金Ⅴ. ACKNOWLEDGMENTS This work was supported by the Chinese Academy of Sciences, the Natural Science Foundation of China (No.20533040), the National Basic Research Program of China (973) (No.2007CB815204m), and the Ministry of Science and Technology of China (No.2007DFA61310).
文摘The pyrolysis of pyridine (5.26% pyridine in argon) was performed with tunable synchrotron vacuum ultraviolet photoionization and molecular-beam mass spectrometry technique at the temperature range of 1255-1765 K at 267 Pa. About 20 products and intermediates, containing major species H2, HCN, C2H2, C5H3N, C4H2, and C3H3N, were identified by near-threshold measurements of photoionization mass spectra and their mole fractions vs. temperatures were estimated. The major reaction pathways are analyzed based on the experimental observations.
基金supported by the National Natural Science Foundation of China(No.91544105,No.41275127,No.U1532137 and No.11575178)。
文摘Vacuum ultraviolet(VUV)photoionization and photodissociation of methylcyclohexane have been studied utilizing a reflectron time-of-flight mass spectrometer(RTOF-MS)with synchrotron radiation source.Photoionization efficiency curves(PIEs)of molecule ion C7H14^+ and fragment ions C7H13^+,C6H11^+,C6H10+,C5H10^+,C5H9^+,C4H8^+,C4H7^+,and C3H5^+ were observed.The ionization energy of methylcyclohexane was measured to be(9.80±0.03)eV,and appearance energies of fragment ions were determined from the PIEs.Optimized structures of transitional states,intermediates and product ions were characterized at the B3LYP/6-31G(d)level and the energies were calculated using G3B3 method.Formation channels of dominating fragment ions were proposed.Intramolecular hydrogen migrations and carbon ring-opening were the foremost processes in fragmentation pathways of methylcyclohexane.
基金supported by the National Natural Science Foundation of China (No.91544105, No.U1532137, No.U1232209, and No.11575178)
文摘The dissociative photoionization of cyclopentanone was investigated by means of a reflectron time-of-flight mass spectrometer(RTOF-MS)with tunable vacuum ultraviolet synchrotron radiation in the photon energy range of 9.0~15.5 eV.The photoionization efficiency(PIE)curves for molecular ion and fragment ions were measured.The ionization energy of cyclopentanone was determined to be 9.230.03 eV.Fragment ions from the dissociative photoionization of cyclopentanone were identified as C5H7O+,C4H5O+,C4H8+/C3H4O+,C3H3O+,C4H6+,C2H4O+,C3H6+,C3H5+,C3H4+,C3H3+,C2H5+and C2H4+.With the aid of the ab initio calculations at theωB97X-D/6-31+G(d,p)level of theory,the dissociative mechanisms of C5H8O+are proposed.Ring opening and hydrogen migrations are the predominant processes in most of the fragmentation pathways of cyclopentanone.
基金supported by the National Natural Science Foundation of China(No.91544105,No.U1532137,No.275127,No.U1232130,No.U1232209,and No.U11575178)the Supercomputing Center of USTC is also acknowledged
文摘The photoionization and dissociation of 2-methyl-2-propen-1-ol(MPO)have been investigated by using molecular beam experimental apparatus with tunable vacuum ultraviolet synchrotron radiation in the photon energy region of 8.0-15.5 eV.The photoionization efficiency(PIE)curves for molecule ion and fragment ions:C4H8O^+,C4H7O^+,C3H5O^+,C4H7^+,C4H6^+,C4H5^+,C2H4O^+,C2H3O+,C3H6^+,C3H5^+,C3H3^+,CH3O^+,CHO^+have been measured,and the ionization energy(IE)and the appearance energies(AEs)of the fragment ions have been obtained.The stable species and the first order saddle points have been calculated on the CCSD(T)/cc-pvTZ//B3LYP/6-31+G(d,p)level.With combination of theoretical and experimental results,the dissociative photoionization pathways of 2-methyl-2-propen-1-ol are proposed.Hydrogen migrations within the molecule are the dominant processes in most of the fragmentation pathways of MPO.
基金Ⅵ. ACKN0WLEDGMENTS This work was supported by the National Natural Science Foundation of China (No.20473081 and No.20533040), and Chinese Academy of Sciences. The authors are also thankful for the valuable help in the experimental work from Aigou Zhu. Fei Qi thanks the Combustion Research Facility of Sandia National Labs to provide a Chemkin program package for kinetic modeling study.
文摘A comprehensive experimental study of the premixed ethylene/oxygen/argon flame at 2.667 kPa with a stoichiometric equivalence ratio (Ф=1) was performed with the tunable synchrotron photoionization and molecular-beam sampling mass spectrometry techniques. The isomers of most observed species in the flame were unambiguously identified by measurements of the photoionization etticiency spectra, e.g. C3H4, C2H4O and C4H4. The mole fraction profiles of species up to C7H8 were measured by scanning the burner position at the selected photon energies near ionization thresholds, and the flame temperature profile was obtained by using Pt/Pt-13%Rh thermocouple. Compared with the previous studies, a lot of new flame species: C3H2, C3H3, C3H5, C2H6O, C4H2, C4H4, C4H6, C3H4O, C3H6O, C3H8O, C5H6, C4H8O and C7H8, were observed. A series of free radicals in the flame are detected to be CH3, C2H3, C2H5, HCO, C3H3 and C3H5. Based on the experimental work, a reduced reaction mechanism was developed including 40 species and 223 reactions. Modeling and measurements agree well for the major species and most intermediates. A detailed kinetic model is desired for this flame.
文摘Molecular frame photoemission is a very sensitive probe of the photoionization (PI) dynamics of molecules. This paper reports a comparative study of non-resonant and resonant photoionization of D2 induced by VUV circularly polarized synchrotron radiation at SOLEIL at the level of the molecular frame photoelectron angular distributions (MFPADs). We use the vector correlation method which combines imaging and time-of-flight resolved electron-ion coincidence techniques, and a generalized formalism for the expression of the Ⅰ(χ, θe, Фe) MFPADs, where χ is the orientation of the molecular axis with respect to the light quantization axis and (θe, Фe) the electron emission direction in the molecular frame. Selected MFPADs for a molecule aligned parallel or perpendicular to linearly polarized light, or perpendicular to the propagation axis of circularly polarized light, are presented for dissociative photoionization (DPI) of D2 at two photon excitation energies, hv=19 eV, where direct PI is the only channel opened, and hv=32.5 eV, i.e. in the region involving resonant excitation of Q1 and Q2 doubly excited state series. We discuss in particular the properties of the circular dichroism characterizing photoemission in the molecular frame for direct and resonant PI. In the latter case, a remarkable behavior is observed which may be attributed to the interference occurring between undistinguishable autoionization decay channels.
基金This work wass supported by the National Natural Science Foundation of China (No.20675074 and No.10575099).
文摘A novel analysis approach using atomic fluorescence excited by synchrotron radiation is presented. A system for synchrotron radiation-atomic fluorescence spectrometry is developed, and experimental conditions such as flow rate, analyte acidity, concentration of pre-reducing and hydrogenation system are optimized. The proposed method is successfully applied to get an excitation spectrum of arsenic. Seven of ten primary spectral lines, four of which have never been reported by means of atomic fluorescence spectrometry, agree well with the existing reports. The other three are proposed for the first time. Excitation potentials and possible transitions are investigated. Especially for the prominent line at 234.99 nm, the mechanism of generation is discussed and a model of energy transition processes is proposed.
文摘The authors synthesized very pure dimer phase of coroneae by simple heat-treatment and subsequent sublimation purification. It was confirmed by laser desorption/ionization mass spectroscopy measurements that pure dimer phase of coronenes can be obtained by controlling the fusing and sublimation temperatures. The crystal structure of the dimer phase was analyzed by synchrotron XRD (X-ray diffraction) experiments. It was also found that very bright red light is emitted by irradiating ultra violet light (λ = 350 nm) to the dimer phase. The external and internal quantum yields were determined to be 5.56% and 6.95%, respectively.
文摘The NSLS-II (National Synchrotron Light Source II) is a state-of-the-art 3 GeV third generation light source currently under integrated testing and commissioning at Brook_haven National Laboratory. The vacuum systems are monitored by vacuum gauges and ion pump current. The gate valves are controlled by PLC (programmable logic controllers) using voting scheme. EPICS (Experimental Physics and Industrial Control System) application codes provide the high level monitoring and control through the input-output controllers. This paper will discuss the commissioning status of the various aspects of vacuum control system.
文摘The binding of (-)-epigallocatechin-3-O-gallate (EGCG) to bovine serum albumin (BSA) were investigated for the first time with spectral methods, including fluorescence and absorption spectrometry under simulative physiological conditions. A strong fluorescence quenching reaction of EGCG to BSA was observed. It was proved that the fluorescence quenching of BSA by addition of EGCG was a result of the formation of EGCG-BSA complex. The binding constant K and the number of binding sites n were determined at physiological conditions and three different temperatures with fluorescence quenching method. The binding distance R and transfer efficiency E between BSA and EGCG were also obtained according to Forster theory of non-radiation energy transfer. The effects of Al^3+, Cu^2+, Mg^2+ and Fe^2+ on the binding constant between EGCG and BSA were studied at 298 K. The effect of EGCG on the conformation of BSA was also analyzed by synchronous fluorescence spectroscopy. PACS. 21. 10. Dr; 32. 50. +d; 32. 30. Jc; 82.80. Dx
文摘The 3rd generation synchrotron light source requires high level of electron beam orbit stability.Shanghai Synchrotron Radiation Facility (SSRF) is a 3rd generation light source under construction;its orbit stability requirement is up to micro or sub-micro range.The storage ring mechanical components vibration caused by the ground motion would influence the orbit stability.The ground motion of SSRF is severe.It is essential to control the vibration of the mechanical components.Vibration damping is an effective method to control the vibration.The author designed a vibration damping structure for the SSRF mechanical components.The test results show that it can effectively control the mechanical vibration.
文摘In this paper,the slow orbit feedback system of HLS,including the feedback principle,the hardware,the software and the main operation results,is briefly introduced.With the help of slow orbit feedback system,the vertical orbit stability of HLS is better than 30 microns,which meets the requirement of synchrotron radiation users and is comparable with the international advanced level of orbit stability in the same kind of machines.
文摘PSD yield is a key criterion to evaluate the vacuum chamber material and its surface pretreatment in an electron storage ring.In this paper,a stainless steel vacuum chamber of 1500 mm in diameter has been tested before and after TiN film coating on PSD experiment station of Machine Study Beamline of NSRL.Test results show that TiN film coating is an effective method to reduce photon stimulated desorption for the stainless steel material.