Barrier-free intermolecular proton transfer in the uracil-glycine complex induced by excess electron attachment

The photoelectron spectra (PES) of anions of uracil-glycine and uracil-phenylalanine complexes reveal broad features with maxima at 1.8 and 2.0 eV. The results of ab initio density functional B3LYP and second order M?ller-Plesset theory calculations indicate that the excess electron occupies a π^* orbital localized on uracil. The excess electron attachment to the complex can induce a barrier-free proton transfer (BFPT) from the carboxylic group of glycine to the O8 atom of uracil. As a result, the four most stable structures of the anion of uracil-glycine complex can be characterized as the neutral radical of hydrogenated uracil solvated by the anion of deprotonated glycine. The similarity between the PES spectra for the uracil complexes with glycine and phenylalanine suggests that the BFPT is also operative in the case of the latter anionic species. The BFPT to the O8 atom of uracil may be related to the damage of nucleic acid bases by low energy electrons because the O8 atom is involved in a hydrogen bond with adenine in the standard Watson-Crick pairing scheme. Received 6 April 2002 Published online 13 September 2002     

In search of new resonance structures in dissociative photoionization of H2

We present a theoretical study of dissociative photoionization of H₂ via the ¹Π_u symmetry in the photon energy range 30–43 eV. Our results explain the various peaks observed in the experiments below 40 eV and illustrate, in particular, the important role of the ²Π_u(2pπ_u) ionization threshold. At higher photon energies, they suggest the existence of new resonance structures that may be associated with doubly excited states of H₂ lying above the third and fourth ionization thresholds (the Q₃ and Q₄ resonance series). From the calculated resonance parameters, we conclude that the dominant mechanism at high photon energies should involve the Q₄ (and probably higher) doubly excited states of H₂. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2002     

A numerical basis for the accurate representation of the continuum spectrum of atomic Hamiltonians

We present a method for the accurate calculation of the complete spectrum of the Schrödinger equation in terms of B-splines polynomial basis. The method is capable to represent numerically the bound and continuum spectrum of complex atomic systems. The theoretical method is discussed, and an application to hydrogenic Hamiltonian is given.AMS subject classification: 65705, 34L40     

利用静电场中光电离效率谱精确确定1,3-二乙氧基苯分子的电离能

电离能是原子和分子的重要的特性参数,在光物理和光化学过程中起着重要作用,精确电离能对相关研究具有重要意义.电离能是调试零动能光谱信号的重要参考数据,在判断异构物数量和分子构型方面也起着关键作用.1,3-二乙氧基苯是一种重要的苯的衍生物,实验证实在超声分子束中包含两种旋转异构物I(down-up)和III(down-do...     

150 fs~10 ps脉宽下熔石英激光损伤的仿真与分析

基于约化电子数密度增长速率方程,建立了熔石英导带电子数密度随脉冲持续时间变化的模型。利用电子数临界密度这一概念,得到了150 fs~10 ps脉宽下,熔石英激光损伤阈值范围。分析表明,5~10 ps,雪崩电离仍然起主要作用,而光致电离提供的初始电子使雪崩电离不再依赖材料原有的初始电子;当脉宽减小到约为4 ps时,光致电离与雪崩电离作用相等;之后,光致电离起主要作用。通过仿真出的损伤阈值拟合,得到了该脉宽区间下新的脉宽定律：熔石英的损伤阈值正比于脉宽的0.38次方;考虑温度对熔石英损伤阈值的影响,熔石英的损伤阈值正比于脉宽的0.34次方。     

与天体物理相关的光电离等离子体的实验室研究

光电离等离子体在天体物理环境中普遍存在,并且由于与黑洞等致密天体紧密关联而具有重要的研究意义.近年来,随着大功率强激光及Z箍缩技术的发展,在实验室中实现了天体环境中的光电离等离子体和光电离过程的模拟.这为验证光电离理论模型的可靠性和准确性,以及认识天体物理环境中的光电离过程及其物理环境的诊断提供了重要的新手段.文章介绍了与天体物理相关的光电离等离子体的实验室研究进展.     

Harmonic and attosecond pulse enhancement in the presence of noise

<正>In this paper,we theoretically investigate the effect of noise on the photoionization,the generation of the high-order harmonic and the attosecond pulse irradiated from a model He~+ ion.It shows that by properly adding noise fields,such as Gaussian white noise,random light or colored noise,both the ionization probabilities(IPs) and the harmonic yields can be enhanced by several orders of magnitude.Further,by tuning the noise intensity,a stochastic resonance-like curve is observed,showing the existence of an optimal noise in the ionization enhancement process.Finally,by superposing a properly selected harmonic,an intense attosecond pulse with a duration of 67 as is directly generated.     

量子态选择的分子离子解离动力学：阈值光电子-光离子符合成像技术的应用

阈值光电子一光离子符合速度成像技术通过对光电子和符合的光离子同时进行速度聚焦控制,大幅提高了电子和离子的收集效率和离子平动能分辨率,成为开展气相分子光电离和光电离．解离动力学研究的有效工具．利用该技术,我们精确地测量了分子的电离能、离子出现势等重要参数,并且开展了若干具有量子态或内能选择的离子解离动力学研究,描绘了相关势能面存在浅势阱等重要动力学特征,讨论了不同振动态和电子态的激发对解离机理和产物通道的重要影响．     

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.