环戊酮C_5H_8O的同步辐射真空紫外光电离解离研究

利用同步辐射光源,研究了环戊酮(C5H8O)在真空紫外105～140 nm波段的光电离和光解离过程.通过质谱测量各离子的光电离效率曲线,得到了该分子的垂直电离能及主要碎片离子的出现势.从理论上利用G3方法,计算了母体和中性及离子碎片的结构和能量,估算了各解离通道所需的解离能.结合实验测量值和理论计算值,指认出环戊酮分子可能的光电离解离通.     

飞秒强激光场中分子双电离的半经典动力学模拟

文章介绍了超短强激光场中原子、分子双电离的研究现状,提出了能够有效处理双电离过程的半经典模型,成功地重现了双电离率随激光强度变化的实验数据,同时预言了分子取向对双电离率的重要影响.文章还通过分析典型的双电离轨道的演化,给出了理解双电离复杂动力学过程的直观物理图像.     

基于多组态含时Hartree-Fock方法研究电子关联对于H_2分子强场电离的影响

发展了三维的处理双原子分子非微扰电子动力学的多组态含时Hartree-Fock方法,并利用该方法研究了电子关联对于H_2分子强场电离概率的影响.该方法采用能够精确处理双中心库仑势的椭球坐标系,以及减小双电子积分计算量的有限元-离散变量基函数方法.利用多组态含时Hartree-Fock方法计算了H_2分子随分子取向角度变化的XUV光电离结果,并通过与单组态结果的对比研究了电子关联对于单电离和双电离概率的不同影响.研究表明,电子关联对于单电离过程影响很小,而在双电离过程中则发挥了重要作用,导致了电离概率的减小.该方法为进一步研究强场物理过程中的电子关联效应奠定了基础.     

双波长圆偏振光场中分子电离动力学的研究新进展

超短激光脉冲的出现为人们研究原子分子内电子的超快动力学过程提供了重要的技术手段。强激光诱导原子分子的光电离过程是光诱导物理过程的基石,也是目前强场物理领域的前沿热点之一。本文重点综述了双波长圆偏振光场中分子电离动力学的研究进展。首先,介绍了研究强场分子电离动力学的半经典模型,给出了电离电子波包的相位和振幅分布。然后,介绍了利用双波长圆偏振光场测量H2分子和CO分子的电离动力学的研究,发现电离电子的振幅结构以及隧穿后电子受到的长程库仑势都会影响电子的动力学过程。此外,电子波包的相位结构也会包含在光电子的发射角中,这个初始相位编码了电子吸收光子而电离过程中的时域信息。最后,对新型阿秒钟在分子光电离过程中的应用进行了总结,并展望了未来复杂分子体系的应用前景。     

激光光解NO2产物--NO分子(XIT)与氧原子O(PJ")的REMPI的离子谱研究

利用激光光解NO2分子,通过共振增强多光子电离(REMPI resonance enhanced multiphoto ionization)及飞行时间(TOF time of flight)质谱技术,获得了振转态分辨的NO(X2Π,υ″,J″)与自旋-轨道分辨的氧原子O(2P3PJ″＝2,1,0)离子谱.NO分子与O原子的离子信号强度与UV电离激光能量之间的关系分别能用二次方和三次方曲线很好拟合,它表明:光解产物NO分子和氧原子是分别通过(1+1)和(2+1)多光子吸收过程而被电离的.由氧离子信号得到的氧原子基态三个自旋-轨道支能级布居比f1与f0分别为0.54±0.09和 0.20±0.04,这一比值与统计分布计算的值为0.6和0.2一致.     

TrpH—TryOH肽链中电子的逆向转移

本文较详细的研究了色氨酰酪氨酸二肽（ＴｒｐＨ－ＴｙｒＯＨ）中的电子转移，电子该电子转移的速率，甚至电子转移的方向都强烈的依赖于溶液的ｐＨ。而且，该肽中的酪氨酸残基瞬态粒子浓度与色氨酸残基瞬态粒子浓度之比也强烈的依赖于ｐＨ。根据这种依赖性，求得了二肽中的ｐＫａ（ＴｒｐＨ＾＋）和ｐＫａ（ＴｙｒＯＨ），其值分别为６．２和１１．３。     

飞秒光物理与介观光学研究获新进展

 北京大学“飞秒光物理与介观光学”创新研究群体采用周期量级飞秒激光系统和冷靶反冲离子动量谱仪装置,首次在实验中通过改变周期量级飞秒激光的载波相位,实现对一氧化碳分子二价电离态的非对称解离通道的控制,同时也实现分子三价离子的非对称解离通道的控制。通过实验证实在一氧化碳分子电离和解离过程中,电子再碰撞激发引起的解离以及电子再碰撞引起电离是主要过程,这两个过程是相互竞争的,并可通过改变激光脉冲载波相位进行调控。该研究工作表明,通过超快光场控制电子再散射波包与分子离子的相互作用,可以在分子电子态水平上实现对分子高阶电离和解离通道过程的操控。研究工作发表在Physical Review Letters 106,073004（2011）。
研究工作得到国家自然科学基金委“创新研究群体”项目,国家重大基础研究计划（973）项目和北京大学人工微结构和介观物理国家重点实验室的资助。     

十二烷基甜菜碱的界面活性及其体系的相态研究

合成了十二烷基甜菜碱（Ｃ１２ＢＥ），经提纯得到合格的样品，测定其等电为ｐＨ＝４．９，ｐＨ〈４．９，分子带正电，ｐＨ≥４．９，分子呈电中性，研究ｐＨ值对其界面活性的影响，同时还研究了醇的种类，浓度，水的盐度，ｐＨ值等因素对Ｃ１２ＢＥ／醇／水／油体系相态的影响，得到了中相微乳液的特性参数，其中有关ｐＨ对相态的影响的研究很有特点。     

Delayed Ionization and Delayed Detachment in Molecules and Clusters

被激发到电离阈值以上的分子体系的演化依赖于激发态的特征和与连续态的耦合等多种参数. 这些特性主要是与分子体系的复杂性,更准确地说与分子的大小,态密度,内自由度中的耦合强度有关.本文通过Na2的里德堡态的自电离,富勒烯C60的延迟电离,阴离子小团簇的延迟解离研究了在小分子中起主导作用的自电离和在大分子以及团簇中出现的延迟电离之间的转变过程. 由于这些体系中相对较慢的内能转移过程,这些研究是在纳秒激光的激发下进行.     

激光光解NO_2产物—NO分子NO(X~2П)与氧原子O(~3PJ″)的REMPI离子谱研究

利用激光光解NO2 分子 ,通过共振增强多光子电离 (REMPIresonanceenhancedmultiphotoionization)及飞行时间 (TOFtimeofflight)质谱技术 ,获得了振转态分辨的NO(X2 Π ,υ″,J″)与自旋 轨道分辨的氧原子O(2P3PJ″ =2 ,1,0 )离子谱 NO分子与O原子的离子信号强度与UV电离激光能量之间的关系分别能用二次方和三次方曲线很好拟合 ,它表明 :光解产物NO分子和氧原子是分别通过 (1+1)和 (2 +1)多光子吸收过程而被电离的 由氧离子信号得到的氧原子基态三个自旋 轨道支能级布居比f1与f0 分别为 0 .5 4± 0 .0 9和 0 .2 0± 0 .0 4 ,这一比值与统计分布计算的值为 0 .6和 0 .2一致     

Resonant structure due to the 3p→3d transition in the photoionization of Ca+

Many-body perturbation theory has been used to calculate the resonance structure (3p→3d) into the photoionization (4s→kp) for ion Ca⁺. This resonance structure results from the interference between a photoionization process or a photoionization with excitation process and a resonant Auger process. The coupled equation method has been improved to calculate this interference by the summation of specific classes of diagrams of perturbation theory to infinite order. The resonance structure in the region of the 3p threshold is enhanced via a super-Coster–Kronig transition. The theoretical results are in good agreement with experiment.     

Numerical studies of atomic three-step photoionization processes with non-monochromatic laser fields

The atomic selective multi-step photoionization process is a critical step in laser isotope separation. In this work, we study three-step photoionization processes with non-monochromatic laser fields theoretically based on the semi-classical theory. Firstly, three bandwidth models, including the chaotic field model, de-correlation model, and phase diffusion model, are introduced into the density matrix equations. The numerical results are compared with each other comprehensively. The phase diffusion model is selected for further simulations in terms of the correspondence degree to physical practice. Subsequently, numerical calculations are carried out to identify the influences of systematic parameters, including laser parameters (Rabi frequency, bandwidth, relative time delay, frequency detuning) and atomic Doppler broadening, on photoionization processes. In order to determine the optimal match among different systematic parameters, the ionization yield of resonant isotope, and selectivity factor are adopted as evaluation indexes to guide the design and optimization process. The results in this work can provide a rewarding reference for laser isotope separation.     

Resonant circular dichroism of chiral metal-organic complex

A sizable enhancement of the circular dichroism in photoelectron spectroscopy has been measured and computed for the metal complex Δ-cobalt(III) tris-acetylacetonate highest occupied molecular orbital state in the region of the Co 3p→3d Fano resonance. In the resonance the dichroism reaches the maximum value of 5% and even changes its sign as compared to the direct photoionization channel. We ascribe this enhancement to electron correlation processes, namely, with the coupling between discrete excitations and the continuum, which is correctly described in the time dependent density functional theory (TDDFT) framework. These findings open new physical aspects of photoelectron circular dichroism that now can be interpreted not only via the simple direct ionization, but also through more complex electron correlation processes.     

FT-EPR study of the pH dependence of the photochemistry of sesamol in aqueous solution

A Fourier transform electron paramagnetic resonance (FT-EPR) study was made of the photochemistry of 3,4-methylenedioxyphenol (sesamol, SEOH)) in aqueous solution. FT-EPR measurements show that in alkaline (pH 11) solution, pulsed-laser excitation of SECT leads to photoionization giving the hydrated electron and SEO^⋅ free radical. Resonance signals from these paramagnetic species develop with instrument-controlled rise time. They exhibit a low-field emission/ high-field absorption (E/A) CIDEP pattern with the transition from emission to absorption occurring at the resonance of the hydrated electron. It is shown that the spin polarization stems from contributions from the ST₀ radical pair mechanism (E/A) and triplet mechanism (A). From this it is concluded that photoionization of sesamol occurs via the triplet excited state. In neutral and acidic (pH 4–7) aqueous solution, photoexcitation generates SEO^⋅ and cyclohexadienyl-type radicals. In this case, radicals grow in over a period of 1–2 μs and FT-EPR spectra display an E/A pattern with the inversion point in the center. The lowering of the pH of the solution apparently is accompanied by a strong reduction in the relative importance of photoionization. From the FT-EPR data it can be deduced that in neutral and acidic solutions the dominant reaction channel is H-atom transfer. In this respect, the photochemistry of sesamol differs from that of phenol andp-cresol. For these phenols the change in pH does not affect the appearance of the FT-EPR spectra. Apparently, the change in electronic structure caused by the methylenedioxy substituent strongly affects the excited state reactivity of sesamol.     

苯低压热解的光电离质谱和动力学模型 (cited: 3)

研究苯在30 Torr和1360～1820 K下的热解过程．利用同步辐射真空紫外光电离质谱技术对热解产物进行了检测,并对其随温度变化的摩尔分数曲线进行了测量．建立了一个低压苯热解动力学模型,并结合生成速率分析展示了燃料分解和芳烃生长过程中的主要反应网络．结果显示苯的分解主要通过氢提取反应生成苯基进行,部分通过单分子解离反应生成丙炔基或苯基进行,并终止于乙炔、丁二炔及1,3,5-己三炔等具有高热稳定性的聚炔烃类物种的生成．此外,低压苯热解中的芳烃生长过程起始于苯和苯基,并主要受到偶数碳增长机理控制．这是由于奇数碳增长机理所依赖的C5和C7物种在低压苯热解中很难生成．     

偶氮苯的同步辐射光电离研究

用同步辐射光电离质谱与符合技术的相结合测定了偶氮苯光电离效率谱，获得了该分子的电离势，导出了分子和分子离子中某些键的解离能以自由基Ｃ６Ｈ５Ｎ２的电离势。测得了不同光子能量激发下的质谱图，并对不同能量时偶氮苯的解离电离方式进行了分析。     

An alternative view of condensed-phase photoionization

This paper proposes an accurate valuable interpretation scheme to study the evolvement of the photoionization processes from the isolated to the condensed atoms by a unique ab initio method. The variations of the photoionization cross sections of the atomic sodium with the photoelectron energy and the boundary radius of the atomic configuration space are studied in this new scheme by the R-matrix method. The discrepancy in the photoionization spectra of the isolated and the condensed sodium has been explained quantitatively and understood successfully by this alternative view in detail for the first time.     

Diagrammatic Representation of Electronic Correlations in Photoionization Process: Application to Scandium

The conversion rules under which an algebraic expression can be obtained from a corresponding photoionization Goldstone diagram have been given systematically in the present work. The electronic correlations in the photoionization processes then could be studied diagrammatically. The application to atomic scandium shows that the present theoretical scheme can give reasonable photoionization cross sections, which agree well with the experimental results.     

Nondipole parameters of TDCS for electron impact ionization and drag current

A comprehensive study is undertaken of angular distributions of electron knock-out from atomic targets by fast electrons with a small transfer of momentum. The general expressions for the parameters of the triple differential cross-section of impact ionization in the optical limit are derived. The calculated parameters are compared with those of the angular distribution of electrons ejected from an atom in the process of photoionization. In these processes, when the multipole transitions are involved, the one-to-one correspondence between the photoionization and impact ionization parameters disappears. The nondipole transitions lead to the backward/forward asymmetry of the angular distribution of ejected electrons that is absent in the dipole approximation for ionization by both fast electrons and photons. Using the He atom as an example, the character of the asymmetry for these two processes is qualitatively different and the backward/forward asymmetry results in macroscopic directed motion of secondary electrons accompanying the passing of a fast electron beam through gas or plasma. The general formulas for this drag current are derived and applied to gaseous He.