碘代烷烃在532 nm激光作用下多光子电离解离机理

利用５３２ｎｍ的激光对碘代烷烃（碘甲烷、碘乙烷、碘代正丙异丙烷）分子作了多光了电离解离（ＭＰＩＤ）质谱（ＭＳ）研究,在５３２ｎｍ激光作用下,ＣＨ３Ｉ分子吸收５３２ｎｍ激光双光子的能量,进入Ａ带的ＩＡ２态,继续吸收光子上泵浦至电离态形成母体离子ＣＨ３Ｉ,然后再形成碎片离子;而其它几个碘代烷烃吸收双光子的能量进入Ａ带后均形成中性碎片,中性碎片再吸收光子经一系列电离解离形成碎片离子,此外,本文还通过对同     

Multiple Ionization of Free Ubiquitin Molecular Ions in Extreme Ultraviolet Free‐Electron Laser Pulses

The fragmentation of free tenfold protonated ubiquitin in intense 70 femtosecond pulses of 90 eV photons from the FLASH facility was investigated. Mass spectrometric investigation of the fragment cations produced after removal of many electrons revealed fragmentation predominantly into immonium ions and related ions, with yields increasing linearly with intensity. Ionization clearly triggers a localized molecular response that occurs before the excitation energy equilibrates. Consistent with this interpretation, the effect is almost unaffected by the charge state, as fragmentation of sixfold deprotonated ubiquitin leads to a very similar fragmentation pattern. Ubiquitin responds to EUV multiphoton ionization as an ensemble of small peptides.     

Photoelectron Circular Dichroism of Bicyclic Ketones from Multiphoton Ionization with Femtosecond Laser Pulses

Photoelectron circular dichroism (PECD) is a CD effect up to the ten‐percent regime and shows contributions from higher‐order Legendre polynomials when multiphoton ionization is compared to single‐photon ionization. We give a full account of our experimental methodology for measuring the multiphoton PECD and derive quantitative measures that we apply on camphor, fenchone and norcamphor. Different modulations and amplitudes of the contributing Legendre polynomials are observed despite the similarity in chemical structure. In addition, we study PECD for elliptically polarized light employing tomographic reconstruction methods. Intensity studies reveal dissociative ionization as the origin of the observed PECD effect, whereas ionization of the intermediate resonance is dominating the signal. As a perspective, we suggest to make use of our tomographic data as an experimental basis for a complete photoionization experiment and give a prospect of PECD as an analytic tool.     

HCl分子在激光场中的多光子激发

用二次量子化方法讨论了ＨＣｌ分子在激光场中的多光子激发，还包括对ＨＣｌ分子伸缩振动能级的计算，跃迁概率随外场频率的变化及随时间的变化（取光场强度１０~（－８）Ｗ／ｃｍ~２）。     

用共振增强多光子电离方法研究几种含溴化合物的光解

利用飞行时间质谱仪(TOF)和共振增强多光子电离(REMPI)方法, 研究了两种正一溴代烷烃(C₂H₅Br, n-C₃H₇Br)和溴苯(C₆H₅Br)在234及267 nm附近的光解. 测出了这几种含溴化合物在不同波长下光解产物Br^*和Br的分支比N(Br*)/N(Br), 并根据从头计算结果, 解释了这几种含溴化合物光解产物的分支比随光解波长变化的趋势及几个低激发态势能面之间的关系.     

Multiphoton excitation of an ammonia molecule in laser fields

The multiphoton excitation of NH3 in laser fields is discussed using the second quantization and unitary transformations.The stretch-vibration energy spectrum obtained from an optimized Hamiltonian is in good agreement with that of experiments.The changes in transition probabilities with the frequencies of laser fields and the lime-dependent transition probabilities at a field intensity of 1.1×10-8 W/cm2 are presented.Finally,the energy absorption is calculated.     

Multiphoton ionization spectroscopy in surface analysis and laser desorption mass spectrometry

The application of resonance-enhanced multiphoton ionization (REMPI) spectroscopy for the ultrasensitive detection of molecules originating from laser desorption experiments performed on a variety of substrates is reviewed. Laser-induced desorption from surfaces is capable of producing intact gas-phase molecules, even from polar, non-volatile, high-molecular-weight and thermally labile substances. REMPI is a highly efficient and optically selective ionization method, which, coupled with laser desorption allows the direct chemical analysis of complex mixtures, without the need for previous sample purification and separation steps. The use of REMPI spectroscopy is discussed in two contexts: (1) for the direct chemical analysis of complex mixtures, e.g., environmental samples, by laser desorption/laser postionization mass spectrometry and (2) for measurements of internal state distribution of molecules laser-desorbed from sub-monolayers surface films to gain insight into the laser desorption mechanism.Presented at the 13th International Symposium on Microchemical Techniques (ISM), held in Montreux, Switzerland, May 16–20,1994     

(1+1) Resonance‐Enhanced Multiphoton Ionization and Photodissociation Study of CS2 via the 1B2 State

(1+1) resonance‐enhanced multiphoton ionization (REMPI) spectra of CS₂ and molecular dissociation dynamics are investigated using a time‐of‐flight mass spectrometer equipped with velocity imaging detection. The REMPI spectra via a linear‐bent →¹B₂( ) transition are acquired in the wavelength range of 208–217 nm. Each ro‐vibrational band profile of the ¹B₂( ) state is deconvoluted to yield the corresponding predissociative lifetime from 0.3 to 3 ps. Upon excitation at 210.25 and 212.54 nm, the resulting images of S⁺ and CS⁺ fragments are analyzed to give individual translational energy distributions, which are resolved into two components corresponding to the CS+S(³P) and CS+S(¹D) channels. The product branching ratios of S(³P)/S(¹D) are evaluated to be 5.7±1.0 and 9.6±2.5 at 210.25 and 212.54 nm, respectively. Despite the difficulty avoiding the effect of multiphoton absorption, the molecular dissociation channel is verified to prevail over the dissociative ionization channel of CS₂. The anisotropy parameters for the triplet and singlet channels are determined to be ～0.8 and 1.1–1.3, respectively, suggesting that the predissociative state should have a bent configuration with a short lifetime.     

共振增强多光子电离耦合飞行时间质谱研究甲烷脱氢芳构化反应

 采用共振增强多光子电离耦合飞行时间质谱技术，初步探测了甲烷无氧芳构化反应。实验结果表明，该技术具有灵敏度高，质量分辨率高，响应时间快等优点，改变波长能实现对目标产物的实时，高灵敏度检测，并且可以获得所有产物的信息。     

飞秒脉冲作用下氯丙烯的多光子解离和电离动力学

The dissociation and photoionization dynamics of C₃H₅Cl were studied at 200, 400, and 800 nm with femtosecond laser pulses. The time-of-flight mass spectra, laser power index and photoelectron images were recorded. At short wavelength (200 nm), ionization of the parent molecule was found to be the dominant channel, while other ions were generated by the dissociation of C₃H₅Cl⁺. With the shift to long wavelength (e.g., 800 nm), fragment ions became dominant, and were generated through the multiphoton ionization of neutral fragments after the photodissociation of C₃H₅Cl. These results imply that photodissociation plays a significant role at long wavelength, because neutral fragments are supposed to be generated from the intermediate states reached by 800 nm photons. At 400 nm, the dissociation on the intermediate states is also critical, but is not as high as that at 800 nm. Taken together, our results demonstrate that the dissociation/ionization behaviors of allyl chloride are wavelength-dependent, and reveal the complex dynamics of allyl chloride at 200, 400 and 800 nm.     

The Elusive Ketene (H2CCO) Channel in the Infrared Multiphoton Dissociation of Solid 1,3,5-Trinitro-1,3,5-Triazinane (RDX)

Understanding of the fundamental mechanisms involved in the decomposition of 1,3,5-trinitro-1,3,5-triazinane (RDX) still represents a major challenge for the energetic materials and physical (organic) chemistry communities mainly because multiple competing dissociation channels are likely involved and previous detection methods of the products are not isomer selective. In this study we exploited a microsecond pulsed infrared laser to decompose thin RDX films at 5 K under mild conditions to limit the fragmentation channels. The subliming decomposition products during the temperature programed desorption phase are detected using isomer selective single photoionization time-of-flight mass spectrometry (PI-ReTOF-MS). This technique enables us to assign a product signal at m/z=42 to ketene (H₂CCO), but not to diazomethane (H₂CNN; 42 amu) as speculated previously. Electronic structure calculations support our experimental observations and unravel the decomposition mechanisms of RDX leading eventually to the elusive ketene (H₂CCO) via an exotic, four-membered ring intermediate. This study highlights the necessity to exploit isomer-selective detection schemes to probe the true decomposition products of nitramine-based energetic materials.     

一种新型光电离/微型正交加速飞行时间质谱仪的设计和性能测试

介绍了自行研制的光电离/微型正交加速飞行时间质谱仪的设计原理和性能。电离源采用光子能量为10.6 eV真空紫外灯,它可将待测分子电离只产生单电荷母体离子,不产生碎片离子。采用该光电离方法得到的质谱谱图比较简单,气体样品可以不经分离直接进行分析。离子正交引入结构的飞行时间质量分析器有效地提高了质谱分辨率。用32 cm无场飞行管,测量碘甲烷得到的质谱分辨率可达430。在谱图获得频率10 kHz的操作条件下,样品总分析时间20 s,得到苯和碘甲烷的检出限分别为10×10-6,5×10-6。软电离和微型化使得该质谱仪在可挥发性有机物的实时在线监测方面有广泛的应用。     

甲胺分子多光子电离质谱研究

胜多光子电离飞行时间质谱法，利用可调谐脉冲激光器，测得了甲胺分子在不同激光波长和激光功率下的多光子电离和解离产物。母体离子ＣＨ３ＮＨ＾＋２的离解速常数随激光发波长的增大而减小。     

Multiphoton dissociation/ionisation of dimethyl sulphide (CH3SCH3) at 355 and 532 nm

Multiphoton dissociation/ionization has been studied for CH₃SCH₃ at 355 and 532 nm using a time-of-flight mass spectrometer. The major ion signals observed at 355 nm are C⁺, CH₃ ⁺, HCS⁺, CH₂S⁺, CH₃S⁺ and CH₃SCH₃ ⁺. Power dependence studies at 355 nm show a (2+1) REMPI process for the formation of parent ion. Peaks atm/e = 46, 47 and 61 show two-photon laser power dependence whereasm/e = 15 and 45 peaks show four-photon dependence. However, in 532 nm photo-ionisation, no parent ion signal is observed. A peak atm/e = 35 corresponding to SH₃ ⁺ has been observed. SH₃ ⁺ has been suggested to originate from CH₃SCH₂ ⁺ via a cyclic transition state. Photoionisation results of CH₃SCH₃ have been compared with those of CH₃SSCH₃, at these two wavelengths.     

质谱光电离/解离技术和生物分子结构鉴定

质谱是一种广泛应用于化学、生物医学、药学、环境、农业和能源等各领域的分子结构鉴定技术,这种技术通过准确测定分子离子和碎片离子的质量-电荷比来推导分子结构。如何将试样中待测组分有效气化、离子化,转变为具有不同质-荷比的气态离子是质谱仪器和分析方法研究的关键。基于不同物理化学原理的电离、解离方法各有特点,适合不同分析目的。常见的软电离技术一般产生稳定的偶电子离子,往往需要与其他技术联用才能实现分子离子的进一步解离。除了基于碰撞活化和电子得失的两类常见解离方法,光解离技术利用波长/能量可调控的光辐射来使样品分子电离,并引发特定化学键断裂。本文旨在综述不同电离/解离技术,重点探讨近年来发展的红外和紫外光电离/解离技术基本工作原理、仪器特点及其在生物分子(包括有机小分子、蛋白质、核酸和多糖等)结构鉴定中的应用。     

OCS的多光子电离高分辨光电子能谱

硫氧化碳OCS是线性三原子分子，这类小分子的激发态、离子态能级结构、能级之间的相互作用及电离过程，是研究中所关心的问题．Tanaka等[1]和Kopp[2]测量了OCS的VUV吸收光谱，Frey和Schlag等[3]以同步辐射光源，用光电离共振（PIR）谱方法、Kovac[4]和Wang，Shirley等[5]以Hel为电离光源，分别采用传统的光电子能谱和高分辨光电子能谱技术研究了CO2、CS2和OCS分子从电子振动基态吸收单个光子而电离的过程．Yang和Anderson等问为了作选态的离子一分子反应利用可调谐激光rt光子吸收将OCS选择激发到某一中间态，OCS再吸收光子后…     

Multiphoton dissociation of C3F6O

Major characteristics of multiphoton absorption and multiphoton dissociation of hexafluoropropene oxide (HFPO) were studied. Spectral relationships of the average number of IR photons absorbed per molecule and the yield of multiphoton dissociation were determined in the range of 1040-985 cm^–1 at different laser fluences. At the laser line 1025.3 cm^–1, the effect of collisions with buffer gases on the HFPO multiphoton absorption and multiphoton dissociation was studied and theq-factor was determined (q = O.6 at= 0.55J cm^–2). Characteristic features of HFPO decomposition under collisional conditions (p _HFPO> 0.1 Torr) were discussed. An anomalous difference in the values for quantum efficiency of multiphoton dissociation for long-wave and short-wave wings of HFPO absorption band was revealed. A procedure for correlating the experimental and theoretical data on the yield of multiphoton dissociation (when theq-factor is unknown) was suggested, and corresponding calculations were performed for the frequency 989.6 cm^–1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1927–1932, November, 1994.