Experiments and Calculations on Photoionization and Dissociative Photoionization of CH2CO

The dissociative photoionization of molecular‐beam cooled CH₂CO in a region of ?10–20 eV was investigated with photoionization mass spectrometry using a synchrotron radiation as the light source. Photoionization efficiency curves of CH₂CO⁺ and of observed fragment ions CH₂⁺, CHCO⁺, HCO⁺, C₂O⁺, CO⁺, and C₂H₂⁺ were measured to determine their appearance energies. Relative branching ratios as a function of photon energy were determined. Energies for formation of these observed fragment ions and their neutral counterparts upon ionization of CH₂CO are computed with the Gaussian‐3 method. Dissociative photoionization channels associated with six observed fragment ions are proposed based on comparison of determined appearance energies and predicted energies. The principal dissociative processes are direct breaking of C=C and C‐H bonds to form CH₂⁺ + CO and CHCO⁺ + H, respectively; at greater energies, dissociation involving H migration takes place.     

Theoretical Investigation on Photoionization and Dissociative Photoionization of Toluene

The photoionization and dissociation photoionization of toluene have been studied using quantum chemistry methods.The geometries and frequencies of the reactants,transition states and products have been performed at B3LYP/6-311++G (d,p) level,and single-point energy calculations for all the stationary points were carried out at DFT calculations of the optimized structures with the G3B3 level.The ionization energies of toluene and the appearance energies for major fragment ions,C₇H₇⁺,C₆H₅⁺,C₅H₆⁺,C₅H₅⁺,are determined to be 8.90,11.15 or 11.03,12.72,13.69,16.28 eV,respectively,which are all in good agreement with published experimental data.With the help of available published experimental data and theoretical results,four dissociative photoionization channels have been proposed:C₇H₇⁺+H,C₆H₅⁺+CH₃,C₅H₆⁺+C₂H₂,C₅H₅⁺+C₂H₂+H.Transition structures and intermediates for those isomerization processes are determined in this work.Especially,the structures of C₅H₆⁺ and C₅H₅⁺ produced by dissociative photoionization of toluene have been defined as chain structure in this work with theoretical calculations.     

Dissociative Photoionization of 1,2-Epoxyoctane Studied with Synchrotron Radiation

Dissociative photoionization of 1,2-epoxyoctane was investigated by synchrotron radiation vacuum ultraviolet photons in the energy region of 9.8-16.6 eV under ultrasonic molec-ular beam. Dissociative fragment ions were measured with reffection time-of-ight mass spectrometer at di erent photon energies. Appearance potentials of the dominative ion fragments were determined through photoionization efficiency curves. The structures and energies of the parent, ionized and neutral radicals were obtained with G3 calculations. Through comparing the experimental results with the theoretical calculations, we proposed the dissociative channels for the photoionization of 1,2-epoxyoctane.     

Dissociative Photoionization of 1,4-Dioxane with Tunable VUV Synchrotron Radiation

The photoionization and photodissociation of 1,4-dioxane have been investigated with a reflectron time-of-flight photoionization mass spectrometry and a tunable vacuum ultraviolet synchrotron radiation in the energy region of 8.0-15.5 eV. Parent ion and fragment ions at m/z 88, 87, 58, 57, 45, 44, 43, 41, 31, 30, 29, 28 and 15 are detected under supersonic conditions. The ionization energy of DX as well as the appearance energies of its fragment ions C₄H₇O₂⁺, C₃H₆O⁺, C₃H₅O⁺, C₂H₅O⁺, C₂H₄O⁺, C₂H₃O⁺, C₃H₅⁺, CH₃O⁺, C₂H₆⁺, C₂H₅⁺/CHO⁺, C₂H₄⁺ and CH₃⁺ was determined from their photoionization efficiency curves. The optimized structures for the neutrals, cations, transition states and intermediates related to photodissociation of DX are characterized at the B3LYP/6-31+G(d,p) level and their energies are obtained by G3B3 method. Possible dissociative channels of the DX are proposed based on comparison of experimental AE values and theoretical predicted ones. Intramolecular hydrogen migrations are found to be the dominant processes in most of the fragmentation pathways of 1,4-dioxane.     

Molecular Frame Photoemission： Probe of the Photoionization Dynamics for Molecules in the Gas Phase

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.     

Experimental and Theoretical Study on Dissociative Photoionization of Cyclopentanone

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 9.23\begin{document}$\pm$\end{document}0.03 eV. Fragment ions from the dissociative photoionization of cyclopentanone were identified as C\begin{document}$_5$\end{document}H\begin{document}$_7$\end{document}O\begin{document}$^+$\end{document}, C\begin{document}$_4$\end{document}H\begin{document}$_5$\end{document}O\begin{document}$^+$\end{document}, C\begin{document}$_4$\end{document}H\begin{document}$_8^+$\end{document}/C\begin{document}$_3$\end{document}H\begin{document}$_4$\end{document}O\begin{document}$^+$\end{document}, C\begin{document}$_3$\end{document}H\begin{document}$_3$\end{document}O\begin{document}$^+$\end{document}, C\begin{document}$_4$\end{document}H\begin{document}$_6^+$\end{document}, C\begin{document}$_2$\end{document}H\begin{document}$_4$\end{document}O\begin{document}$^+$\end{document}, C\begin{document}$_3$\end{document}H\begin{document}$_6^+$\end{document}, C\begin{document}$_3$\end{document}H\begin{document}$_5^+$\end{document}, C\begin{document}$_3$\end{document}H\begin{document}$_4^+$\end{document}, C\begin{document}$_3$\end{document}H\begin{document}$_3^+$\end{document}, C\begin{document}$_2$\end{document}H\begin{document}$_5^+$\end{document} and C\begin{document}$_2$\end{document}H\begin{document}$_4^+$\end{document}. With the aid of the ab initio calculations at the \begin{document}$\omega$\end{document}B97X-D/6-31+G(d, p) level of theory, the dissociative mechanisms of C\begin{document}$_5$\end{document}H\begin{document}$_8$\end{document}O\begin{document}$^+$\end{document} are proposed. Ring opening and hydrogen migrations are the predominant processes in most of the fragmentation pathways of cyclopentanone.     

二乙基锌的同步辐射真空紫外光电离光解离

利用同步辐射光源和反射式飞行时间质谱, 在超声冷却条件下对二乙基锌(ZnC4H10)进行真空紫外(VUV, 能量范围为8-22 eV)光电离光解离研究. 实验获得ZnC4H10的光电离质谱图; 通过测量各碎片离子的光电离效率(PIE)曲线, 获得ZnC4H10的电离势(IP=8.20±0.05 eV)及其碎片离子(ZnC2H5+、ZnH+、Zn+、C2H5+、C2H3+等)的出现势. 根据实验结果, 并结合相关文献所给的热力学数据, 推导出这些主要碎片离子的生成焓, 并分析它们可能的解离通道和主要离子的分支比. 结果表明, 其主要解离通道是母体离子发生Zn—C 键的断裂形成ZnC2H5+和C2H5+离子, ZnC2H5+离子再进一步解离形成Zn+离子, 并且含锌碎片离子的丰度占75%以上.     

Vacuum Ultraviolet Photoionization and Dissociative Photoionization of Capecitabine, 50-Deoxy-5-'uorocytidine,and 50-Deoxy-5-'uorouridine

Vacuum ultraviolet (VUV) photoionization and dissociative photoionization of capecitabine and its metabolites, 5'-deoxy-5-fluorocytidine (5'-DFCR) and 50-deoxy-5- fluorouridine (5'-DFUR), were investigated with infrared laser desorption/tunable synchrotron VUV pho-toionization 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 de-tail. 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.     

Theoretical Study of Isoprene Dissociative Photoionization

Theoretical calculations have been carried out to investigate the possible dissociation channels of isoprene. We focus on the major fragment ions of C₅H₇⁺,C₅H₅⁺,C₄H₅⁺,C₃H₆⁺,C₃H₅⁺,C₃H₄⁺,C₃H₃⁺ and C₂H₃⁺, which were observed experimentally from the isoprene dissociative photoionization. The energy calculations were performed with the CBS-QB3 model. All the geometries and energies of the fragments, intermediates and transition states involved in the dissociations channels were determined. Finally, the mechanisms of the dissociation pathways were discussed on the comparison of theoretical and experimental results.     

van der Waals团簇ArHCl的光电离研究

用同步辐射光源和光电离质谱研究了分子束中ArHClvanderWaals（vdW）团簇的光电离过程．测量结果表明，分子束中的ArHCl的浓匠与气源压力近似满足如下关系式：a（ArHCl）％＝179×10-8.首次给出了ArHCl团簇的光电高效率曲线，并测得ArHCl 的出现势为12.52±0.03eV。根据实验测量的HCl和ArHCl的电高能，计算出Ar－HCl 的解高能为022±0.03eV.用Gaussian－94w量化程序计算出解高能约为0.16eV.实验表明当团簇内的Ar电离时，ArHCl 质谱峰强度明显低于预计的强度，是由于体系电离后发生了电荷转移及解离过程．     

3-氯-1，2-环氧丙烷的同步辐射光电离

杂环类化合物在自然界中分布十分广泛,且许多具有生物活性,它们大多数在生物的生长 发育、遗传和衰亡过程中起着关键的作用［１,２］．含氧三元杂环体系是最基本、最简单的杂环化合 物,分子中的含氧三员环,具有很大的张力,且存在很强的极性共价键,使其易于发生定向开环 反应,具有高度反应性．利用光电高质谱法对这类分子进行光电离与光离解研究,可以获得这 类物质一些重要的物理化学数据． 我们已对环氧乙烷和环氧丙烷进行了光电离和光离解研究,并结合量化理论计算分析了 它们的光电离解离通道［３,４］,３－氯－１,２－环氧丙…     

乙苯光电离的实验研究

利用真空紫外同步辐射和反射式飞行时间质谱研究了乙苯分子的光电离, 通过测量母体分子的光电离质谱(PIMS)以及母体离子和主要碎片离子的光电离效率曲线(PIEs), 确定了乙苯分子的电离能IE(C8H+10)=(8.66±0.02) eV, 主要碎片离子C7H+7和C6H+6的出现能分别为(10.81±0.02)和(10.99±0.02) eV; 利用经验公式计算出产生碎片离子C7H+7和C6H+6需要的解离能(Ed)分别为(2.15±0.04)和(2.33±0.04) eV. 结合相关的热化学参数, 推算出C8H+10, C7H+7和C6H+6的标准生成焓分别为865.5, 927.2和1037.9 kJ/mol. 为进一步研究乙苯的大气光氧化反应机理提供了参考.     

m-Xylene Isomerization in SAPO-11/HZSM-5 Mixed Catalyst

The catalytic isomerization of m-xylene was studied over a solid acid silicoaluminophosphate type SAPO-11, mixed to HZSM-5 zeolite. The reaction was processed varying the temperature and weight hourly space velocity, using a fixed bed continuous flow reactor. The m-xylene suffers isomerization to p-xylene and o-xylene by molecular displacement of methyl groups. The mixed catalyst was selective to p-xylene at 623 K and 2.5 h⁻¹ with a maximum p/o ratio of 2.05. The ethylbenzene formation was not observed in the products. In this process an apparent activation energy of the order of 13.9 kJ mol⁻¹ was obtained. This revised version was published online in June 2006 with corrections to the Cover Date.     

二甲胺同步辐射光电离解离机理的质谱研究

利用同步辐射光源，结合飞行时间质谱，在超声射流冷却条件下研究了(CH_3) _2NH(DMA)的光电离解离机理。实验观察到四种主要离子(CH_3)_2NH·~+， CH_3NH~+CH_2，CH_2NH_2~+和CHNH~+，质荷比分别为m/z = 45，44，30和28。四种 离子的出现势（AE）分别为8.26，9.52，11.93和11.27 eV，其中分子电离热IP = （8.26 ± 0.01） eV，计算得到分子离子的生成热Δ_fH~o = 778.55 kJ/mol。 分析表明离子CH_3NH~+CH_2来自母体离子的α去H过程。其他碎片离子由后续逐级 解离去H反应以及脱CH_3通道生成。     

氯苯的同步辐射光电离研究

Photoionization studies of chlorobenzene were performed by using a time-of-flight mass spectrometer (TOF-MS) with vacuum ultraviolet (VUV) photons from the Heifei synchrotron radiation source. The photoionization mass spectrum and the photoionization efficiency (PIE) curves of both parent and fragment ions were measured. The appearance potentials of the major ions were obtained from their PIE curves. From these data, the standard formation enthalpies of C6H5Cl+, C6H+5 and C4H+3 were evaluated, some dissociative energy was derived. We will be able to detect chlorobenzen with SPI-TOFMS and 118.0 nm laser light.     

Photoionization Mass Spectrometry: A Useful Method to Evaluate the Pyrolysis Process of Glycoside Flavor Precursor

The thermal decomposition behavior and the pyrolysis products of benzyl‐2,3,4,6‐tetra‐O‐acetyl‐β‐D‐glucopyranoside (BGLU) were studied with synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry at temperatures of 300, 500 and 700 °C at 0.062 Pa. Several pyrolysis products and intermediates were identified by the measurement of photoionization mass spectra at different photon energies. The results indicated that the primary decomposition reaction was the cleavage of O‐glycosidic bond of the glycoside at low temperature, proven by the discoveries of benzyloxy radical (m/z = 107) and glycon radical (m/z = 331) in mass spectra. As pyrolysis temperature increased from 300 to 700 °C, two possible pyrolytic modes were observed. This work reported an application of synchrotron VUV photoionization mass spectrometry in the study of the thermal decomposition of glycoside flavor precursor, which was expected to help understand the thermal decomposition mechanism of this type of compound. The possibility of this glycoside to be used as a flavor precursor in high temperature process was evaluated.     

间硝基苯胺的同步辐射光电离研究

利用同步辐射光电质谱法对间硝基苯脘进行了研究，测得了其电离势ＩＰ为９．６６０．０５ｅＶ，以及一些碎片离子出现势ＡＰ，计算出离解能Ｄ０（Ｎ２Ｏ－Ｃ６Ｈ６Ｎ＾＋）和离子生成焓ΔＨｆ（Ｃ６Ｈ６Ｎ＾＋）。给出了间硝基苯胺的同步辐射同离质谱图，并对主要碎片离子的产生过程进行了初步分析。     

Dissociative photoionization of isoprene: experiments and calculations

Vacuum ultraviolet (VUV) dissociative photoionization of isoprene in the energy region 8.5–18 eV was investigated with photoionization mass spectroscopy (PIMS) using synchrotron radiation (SR). The ionization energy (IE) of isoprene as well as the appearance energies (AEs) of its fragment ions C₅H₇⁺, C₅H₅⁺, C₄H₅⁺, C₃H₆⁺, C₃H₅⁺, C₃H₄⁺, C₃H₃⁺ and C₂H₃⁺ were determined with photoionization efficiency (PIE) curves. The dissociation energies of some possible dissociation channels to produce those fragment ions were also determined experimentally. The total energies of C₅H₈ and its main fragments were calculated using the Gaussian 03 program and the Gaussian‐2 method. The IE of C₅H₈, the AEs for its fragment ions, and the dissociation energies to produce them were predicted using the high‐accuracy energy model. According to our results, the experimental dissociation energies were in reasonable agreement with the calculated values of the proposed photodissociation channels of C₅H₈. Copyright © 2009 John Wiley & Sons, Ltd.