Combined Crossed Molecular Beams and Ab Initio Study of the Bimolecular Reaction of Ground State Atomic Silicon (Si; 3P) with Germane (GeH4; X1A1)

The chemical dynamics of the elementary reaction of ground state atomic silicon (Si; ³P) with germane (GeH₄; X¹A₁) were unraveled in the gas phase under single collision condition at a collision energy of 11.8±0.3 kJ mol⁻¹ exploiting the crossed molecular beams technique contemplated with electronic structure calculations. The reaction follows indirect scattering dynamics and is initiated through an initial barrierless insertion of the silicon atom into one of the four chemically equivalent germanium-hydrogen bonds forming a triplet collision complex (HSiGeH₃; ³ i1 ). This intermediate underwent facile intersystem crossing (ISC) to the singlet surface (HSiGeH₃; ¹ i1 ). The latter isomerized via at least three hydrogen atom migrations involving exotic, hydrogen bridged reaction intermediates eventually leading to the H₃SiGeH isomer i5 . This intermediate could undergo unimolecular decomposition yielding the dibridged butterfly-structured isomer ¹ p1 (Si(μ-H₂)Ge) plus molecular hydrogen through a tight exit transition state. Alternatively, up to two subsequent hydrogen shifts to i6 and i7 , followed by fragmentation of each of these intermediates, could also form ¹ p1 (Si(μ-H₂)Ge) along with molecular hydrogen. The overall non-adiabatic reaction dynamics provide evidence on the existence of exotic dinuclear hydrides of main group XIV elements, whose carbon analog structures do not exist.     

Molecular Photochemistry: Recent Developments in Theory

Photochemistry is a fascinating branch of chemistry that is concerned with molecules and light. However, the importance of simulating light‐induced processes is reflected also in fields as diverse as biology, material science, and medicine. This Minireview highlights recent progress achieved in theoretical chemistry to calculate electronically excited states of molecules and simulate their photoinduced dynamics, with the aim of reaching experimental accuracy. We focus on emergent methods and give selected examples that illustrate the progress in recent years towards predicting complex electronic structures with strong correlation, calculations on large molecules, describing multichromophoric systems, and simulating non‐adiabatic molecular dynamics over long time scales, for molecules in the gas phase or in complex biological environments.     

Dynamics of charge transfer at Au/Si metal-semiconductor nano-interface

An ab initio analysis of the periodic array of Au/Si nanostructure composed of gold clusters linked to silicon quantum dot (QD) co-doped by aluminium and phosphorus along [111] direction is presented in this paper. The density functional theory (DFT) is used to compute the electronic structure of the simulated system. Non-adiabatic coupling implemented in the form of dissipative equation of motion for reduced density matrix is used to study the phonon-induced relaxation in the simulated system. The density of states clearly shows that the formation of Au–Si bonds contributes states to the band gap of the model. Dynamics of selected photo-excitations shows that hole relaxation in energy and in space is much faster than electron relaxation, which is due to the higher density of states of the valence band.     

非绝热壁叶栅的粘性流动

非绝热壁叶栅的粘性流动王正明（中国科学院工程热物理研究所北京１０００８０）关键词非绝热壁；叶栅；粘性流动１引言近年来，随着计算机运算速度的提高，叶轮机械内部粘性流动的数值解法发展很快，对于动量方程，已广泛采用亘接求解不作简化的完全的Ｎ－Ｓ方程，以便更...     

Adiabatic and Non-Adiabatic Berry Phases in Generalized J-C Model of Multi-Photon Process

We derive the adiabatic and non-adiabatic Berry phases in the generalized Jaynes-Cummings model of multi-photon process. The results show that the adiabatic Berry phase is kept a constant π independent of all the parameters, while the non-adiabatic approximate Berry phase is parameter-dependent, proportional to the average photon number m, and tends to be constant with the increasing detuning. In the case of exact n-photon resonance and an integer ratio of m/n, the two results coincide with each other, otherwise there appears an additional non-trivial phase factor.     

H++CO2散射在30电子伏能量下电荷转移和非电荷转移的非绝热分子动力学模拟

在大气化学、天体物理学和癌症质子疗法中都涉及到高能H⁺+CO₂散射反应.本文在最简电子-核动力学（SLEND）基础上系统研究在30 eV下的H⁺+CO₂散射.SLEND用经典力学描述核,用单行列式Thouless波函数描述电子.本文模拟了CO₂在42个取向共3402条轨线,为理解H⁺+CO₂散射中的各个反应过程和机制提供了系统描述：非电荷转移散射（NCTS）,电荷转移散射（CTS）和C=O双键的断裂,这些关于反应的有用信息不能完全从实验中获取.本文提供了散射的详尽细节,包括随CO₂取向不同主彩虹角和次彩虹角的出现和合并.SLEND NCTS和CTS的微分散射截面通过高等半经典方法计算,显示NCTS散射截面对所有散射角都同实验符合得很好,而CTS散射截面只大散射角时同实验结果符合得很好而在小角散射时稍差.无论是CTS还是NCTS SLEND都预言了主彩虹角的特征,这同实验完全一致.     

Reduced classical trajectory equations for electronically non-adiabatic transition on photochemical pericyclic reactions

It may be difficult to use the classical trajectory equations (CTE) for the estimation of electronically non-adiabatic transition probabilities in photochemical pericyclic reactions because of many nuclear degrees of freedom. In order to avoid this difficulty, the CTE were reformulated in terms of the reaction path coordinates, and the reduced CTE were derived, in which the system was restricted to move one-dimensionally along the postulated reaction path. As an application, the non-adiabatic decay from the lowest excited state to the ground state was investigated for the conrotatory and disrotatory processes of the photochemical electrocyclic reaction of 1,3-cis-butadiene to form cyclobutene.     

Adiabatic and Non-Adiabatic Berry Phases in Generalized J-C Model of Multi-Photon Process

We derive the adiabatic and non-adiabatic Berry phases in the generalized Jaynes-Cummings model of multi-photon process. The results show that the adiabatic Berry phase is kept a constant π independent of all the parameters, while the non-adiabatic approximate Berry phase is parameter-dependent, proportional to the average photon number m, and tends to be constant with the increasing detuning. In the case of exact n-photon resonance and an integer ratio of m/n, the two results coincide with each other, otherwise there appears an additional non-trivial phase factor.     

从随机到取向--分子转动动力学的超快调控

分子取向物理是研究如何操控分子空间排列方向以及如何制备具有特定方向的分子。近十多年来,分子取向物理学取得巨大进展,人们通过各种技术对分子取向物理进行研究,使人们对分子取向的认识达到一个全新的高度。文章首先介绍了分子的量子态及其分布,转动量子态选择方法和分子的转动动力学,然后概述通过制备和调控转动态的相干布居来控制分子取向的方法。实验和理论表明,分子的不同转动态在相同激光条件作用下产生的转动波包不一样,从而导致分子的准直和取向程度随时间演化完全不一样。通过选择合适的转动量子态能够很好地提高分子取向程度。取向分子作为相互作用靶,为原子分子动力学、精密测量物理、立体化学反应和表面碰撞过程等提供了更加丰富多彩的研究内容。