Determination of dissociative limit of NO2 and characteristics of a molecular beam by fluorescence excitation spectra

Fluorescence excitation spectra are used to determine the onset of predissociation of rotationally cooled NO₂ with an accuracy of 0.2 meV. The divergence and velocity distribution of the molecular beam are measured using only time-resolved and time-integrated fluorescence spectra. This eliminates the need for a separate velocity selector and mass spectrometer.     

Velocity imaging spectrometer for negative fragment ions: application to dynamics of O2 and N2O ion-pair dissociation

A velocity imaging spectrometer has been developed to observe negative ions from molecular ion-pair dissociation. The imaging spectrometer is equipped with a pair of permanent magnets. The resulting magnetic field prevents efficiently the electrons from reaching the detector, without seriously affecting negative ions’ trajectories. The performance of the imaging spectrometer is demonstrated by the observations of photoelectrons from O₂ and He, and O⁻ from O₂. Application to ion-pair dissociation of O₂ and N₂O is presented, and it proves that the present imaging method provides useful information on the assignments of superexcited states and on the dynamics of ion-pair dissociation.     

Intracavity laser spectroscopy of CH<Subscript>4</Subscript> and NH<Subscript>3</Subscript> gases by using a pulse-periodic Cr<Superscript>2+</Superscript>:ZnSe laser

The results of studying the characteristics of an intracavity laser spectrometer based on a polycrystalline Cr²⁺:ZnSe laser operating in a pulse-periodic regime with the pulse-repetition rate of 3 kHz and pulse duration of ∼50 ns are presented. Intracavity spectra of absorption of NH₃ and CH₄ gases in the vicinity of 2.35 μm are measured. The estimate of the spectrometer sensitivity is provided.     

Low-temperature time-resolved vacuum UV spectroscopy of NH<Subscript>4</Subscript>H<Subscript>2</Subscript>PO<Subscript>4</Subscript> crystals

A complex investigation of the dynamics of electronic excitations in nonlinear optical crystals of ammonium dihydrophosphate NH₄H₂PO₄ was performed using low-temperature vacuum UV luminescence spectroscopy with time resolution upon selective photoexcitation by synchrotron radiation. Data on the photoluminescence decay kinetics, time-resolved photoluminescence spectra (2–6.2 eV), and time-resolved photoluminescence excitation spectra (4–24 eV) were obtained for the first time for NH₄H₂PO₄ crystals at 8 K. It is ascertained that the photoluminescence of NH₄H₂PO₄ crystals in the vicinity of 4.7 eV has intrinsic character due to the radiative annihilation of self-trapped excitons. Possible channels of generation and decay of relaxed and unrelaxed electronic excitations in NH₄H₂PO₄ crystals are discussed.     

Accurate determination of the relative concentrations of ammonia isotopologues in a cold,electrostatically guided molecular beam

Buffer-gas cooling and electrostatic velocity selection techniques are combined in this work to produce a continuous molecular beam with rotational and translational temperatures comparable to those in the interstellar medium (ISM). A number of different mixtures of the isotopologues of ammonia (ND₃, ND₂H, NH₂D and NH₃) in varying ratios are used as the source gas, and the molecular beam emanating from the quadrupole guide velocity selector is characterised using mass spectrometry and Monte Carlo trajectory simulations. The guiding of the mixed isotopologues ND₂H and NH₂D is demonstrated for the first time. This approach establishes both the relative concentrations of each species in the beam and the internal rotational state distributions after buffer-gas cooling and guiding. Such information is essential for experiments in which the beam is used in reaction rate measurements (e.g., for ion–molecule reactions) and facilitates the study of reactions relevant to deuterium fractionation in the ISM, such as the competition between H and D transfer with mixed species including ND₂H and NH₂D.     

Photoelectron spectroscopy of size-selected cluster ions using synchrotron radiation

A new experimental setup for photoelectron spectroscopy of size-selected cluster ions using synchrotron VUV radiation as generated by the Swiss Light Source is presented. An intense positively charged cluster ion beam is produced in a high-intensity magnetron sputter source. The clusters are subsequently mass selected in a sector magnet. To maximize the residence time of the cluster ions in the ionization region of the velocity map imaging spectrometer, the cluster ion beam is decelerated where it crosses the light beam. First experiments on (MoO₃) _n ⁺ (n = 69 and 59) cluster cations show that the approach is capable of delivering photoelectron spectra of size-selected transition metal cluster ions.     

紫外光诱导光电子发射负离子源的阈值光电子成像仪设计 (cited: 2)

设计了一套紧凑的光电子成像装置,它包括解离式光电子贴附负离子源、垂直安装的高分辨阈值光电子速度成像装置和线性飞行时间质谱仪．紫外光辐射金属表面诱导低能光电子发射,再通过低能电子贴附超声分子束产生高强度和冷的负离子源．结合这种负离子源和飞行时间质谱-光电子成像仪装置,仪器的质量分辨能达到200左右,能量分辨优于3%(即对1 eV动能的电子,分辨达到30 meV)．此外,使用该实验装置获得了CH₃S^-和S₂^-在611.46 nm下的低能阈值光电子成像结果．同时得到了CH₃S和S₂的更精确的电子亲和势分别为1.8626±0.0020和1.6744±0.0035 eV．初步的结果证明了该装置对研究阈值光电子成像精确测量光电子亲和势非常有效     

Time-dependent delayed electron spectra: a direct measurement of total decay rate as a function of internal energy

We present a general method to measure internal energy dependant decay rate in the case of systems emitting thermal electrons. Our approach is based on the measurement of the time-dependent kinetic energy spectra of delayed electrons using time-resolved velocity map imaging spectrometry. We illustrate this method in the case of C₆₀ molecules. Indeed electron spectra for C₆₀ have been studied in great details in the past few years, allowing a complete analysis of the observed features. Moreover, C₆₀ offers the opportunity to study competing decay mechanisms demonstrating that the technique may have broader applicability to other molecules. Using a model that includes all contributing decay channels relevant in our time delay range (namely delayed ionization and dissociation by C₂ emission) we are able to derive quantitative information on the decay channels of the molecule. In the situation considered here, the time-dependent electron temperature extracted from the kinetic energy spectra is used to determine more precisely the rate constant for the dominant process, namely neutral C₂ dissociation channel. In other words, the measurement of the cooling of an ensemble of C₆₀ molecules as a function of time delay after heating provides a direct and quantitative access to its decay dynamics. This method may be used to map out the total rate for complex decay mechanisms.     

Characterizing ammonia and nitric oxide interaction with outwardly propagating spherical flame method

With the growing attention on ammonia (NH₃) combustion, understanding NH₃ and nitric oxide (NO) interaction at temperatures higher than DeNOx temperature region or even flame temperature becomes a new research need. In this work, the outwardly propagation spherical flame method was used to investigate the laminar flame propagation of NH₃/NO/N₂ mixtures and constrain the uncertainties of the specific kinetics. The present experiments were conducted at initial pressure of 1 atm, temperature of 298 K and equivalence ratios from 1.1 to 1.9. A kinetic model of NH₃/NO combustion was updated from our previous work. Compared with several previous models, the present model can reasonably reproduce the laminar burning velocity data measured in this work and speciation data in literature. Based on model analyses, the interaction of NH₃ and NO was thoroughly investigated. As both the oxidizer and a carrier of nitrogen element, NO frequently reacts with different decomposition products of NH₃ including NH₂, NH and NNH, and converts nitrogen element to the final product N₂. It is found that the laminar burning velocity experiment of NH₃/NO/N₂ mixtures using the outwardly propagating spherical flame method can provide highly sensitive validation targets for the kinetics in NH₃ and NO interaction.     

用于团簇负离子的共线光电子速度成像仪

描述了包含共线的光电子速度成像仪,以及与双阀激光溅射团簇源联用的时间飞行质谱装置．为了避免预混气体,两个脉冲阀和一个反应通道被用来产生反应负离子．共线的光电子成像仪采用了改进的速度成像透镜系统,它的能量分辨率优于3%．此外还报道了Si₄^-团簇在532和355 nm,以及Si₃C^- 团簇在532 nm的光电子速度成像．从实验图像中可以获得光电子能谱和各向异性参数．从Si₄^-团簇能谱上获得了中性的Si₄团簇的基态和第一激发态的振动频率分别为330和312 cm^-1．初步的实验结果证明这套光电子成像装置对研究团簇负离子的电子结构以及光脱附动力学非常有效.