A Comprehensive Therotical Investigation of Intramolecular Proton Transfer in the Excited States for Some Newly-designed Diphenylethylene Derivatives Bearing 2-(2-Hydroxy-Phenyl)-Benzotriazole Part

This article presents a comprehensive therotical investigation of excited state intramolecular proton transfer (ESIPT) for some newly-designed diphenylethylene derivatives containing 2-(2-hydroxy-phenyl)-benzotriazole moiety with various substituted groups. The calculation shows the structural parameters and Mulliken charges of phototautomers enol (E) and keto (K) of these compounds exhibit no or tiny changes from S₀ to S₁. The calculated results suggest that HOMO and LUMO + 1 of the compounds displays excellent overlapping nature, and thus the absorption and emission could be from the electron transition of HOMO→LUMO + 1. The electron density distribution in the frontier orbital of E and K are influenced remarkably by various substituted groups in S₀ and S₁ states. Electron density distribution deficiency in 2-(2-hydroxy-phenyl)-benzotriazole part is observed in L + 1 for these derivatives. The calculation also suggests the potential energy curves of ESIPT are shown to be a strong relationship with electron donor-acceptor groups. The absorption spectra, normal emission spectra and ESIPT spectra of the derivatives were also calculated.     

Image states and excitons at insulator surfaces with negative electron affinity

We discuss electronic excitation processes at two ionic insulator surfaces, LiF(001)-(1x1) and MgO(001)-(1x1), within ab initio many-body perturbation theory. Because of the negative electron affinity of the surfaces, the lowest unoccupied electronic states are image states located in the vacuum outside the surface. Excitations of electrons from the surface layer into these image states are much lower in energy than the bulk excitons. They are responsible for characteristic surface features in the electron energy-loss spectra of LiF(001) and MgO(001).     

甲烷分子电子碰撞电离和解离的实验研究

本文利用反应显微成像技术(reaction microscope)研究了54 eV电子入射甲烷分子导致的电离解离过程,详细分析了电离解离产生的CH⁺₂,CH⁺,C⁺离子碎片的动能分布情况.实验结果表明,该入射能量下产生CH⁺₂,CH⁺,C⁺离子碎片主要贡献来自2a₁内价轨道电子的直接电离过程产生的离子态(2a< 关键词： 反应显微成像谱仪 电离解离 能量沉积 动能分布     

Vibronic spectra, ab initio calculations, and structures of conformationally non-rigid molecules of oxalyl halides in the ground and lowest excited electronic states. Part III: Theoretical investigation of oxalyl fluoride

We present a theoretical investigation of oxalyl fluoride (COF)₂ in the ground and the four lowest excited (two singlet and two triplet) electronic states of the n,π∗-type mainly with the CASPT2(8-6)/cc-pVTZ method. Geometries, vibrational frequencies, potential energy functions of internal rotation, and adiabatic electronic transition energies were obtained. The conformer energy difference and the barrier to internal rotation in the ground electronic state were extrapolated to the complete basis set limit. The planar trans and cis conformations were the most stable configurations for all five electronic states under study. We found that the allowed electronic transition of the cis conformer has a transition energy that is significantly higher than that predicted in previous studies. For the excited states, the internal rotation was found to be accompanied by significant non-planar distortion of both carbonyl fragments, indicating strong coupling between these molecular motions.     

LOW TEMPERATURE OPTICAL PROPERTIES OF AMORPHOUS OXIDE NANOCLUSTERS IN POLYMETHYL METHACRYLATE MATRIX

We studied the temperature-dependent steady-state and time-resolved fluorescence properties of very small (1-2 nm) ZnO, CdO, and PbO amorphous nanoclusters prepared in AOT reverse micelles and imbedded in polymethyl methacrylate(PMMA) films. X-ray diffraction and electron diffraction and imaging indicate that these structures are amorphous. These amorphous oxide nanoclusters demonstrate similar structural, electronic, and optical properties. Properties of steady-state fluorescence spectra indicate the unique localization of electronic states due to the amorphous structure. ZnO and CdO show double-band fluorescence structure, which is due to the spin-orbital splitting, similar to Cu₂O. Time-resolved fluorescence studies of the nanoclusters in the polymer reveal two lifetime components, as found in solution. The slow component reflects relaxation processes from band-tail states while the fast component may be related to high-lying extended states. The temperature dependence of fast fluorescence component reveals the presence of exciton hopping between anharmonic wells at temperatures higher than 200K. We correlate the barrier height between two wells formed around local atoms with the inter-atomic distance and bond ionicity.     

Center-of-mass deflections in two processes: Collision-induced dissociations of 10 keV H 2 + ions in their electronic ground state 1sσ g and dissociative electron capture

By means of a flight-time difference apparatus the two collision induced processes of dissociative vibrational excitations $$H_2^ + (10keV,1s\sigma _g ) + target \to (H_2^ + )*(1s\sigma _g ) \to H^ + + H(1s)$$ and $$H_2^ + (10keV,1s\sigma _g ) + target \to (H_2 )*(unspecified) \to H + H$$ have been determined from an asymmetry in the lab-frame resulting from deflections of the centers-of-mass of the incident projectiles. H⁺+H velocity distributions from vibrational excitations of the electronic ground state of the H ₂ ⁺ ions will be presented which have been directly measured. Competition of any of the higher lying electronically excited states of the projectiles is estimated to be negligible. In the case of dissociative electron capture combined with simultaneous deflections of the centers-of-mass the electronic states of the intermediate H₂ molecules and of the H fragments could not be specified.     

Rate processes in condensed media: Basic equations

A general theory of rate processes is developed. Starting from the first principles, the non-Markovian and Markovian type equations governing relaxation processes are derived. Under certain conditions (which are specified) these equations may be approximately reduced to master equations.The theory is applied to two specific models. In one of them the electron-nuclear system is represented by two intersecting electronic energy hyper-surfaces with a continuum of degrees of freedom plus a small perturbation causing transitions between these electronic states. The equations determining the time behaviour of the electronic subsystem in the general case do not coincide with master equations and the time evolution of the system has mixed oscillatory decaying behaviour.Another model takes into account a possible competition between electronic and vibrational relaxations. The corresponding kinetic equations are derived.     

Properties of oligothiophene polycations

The different electronic states of trications and tetracations have been studied for oligomers made of n 3,4‐ethylenedioxythiophene units, where n ranges from 2 to 30. Results have been compared with those obtained for neutral, monodications and dications of the same n‐oligomers. For the longer oligomer (n ≥ 24) trications, the doublet and quartet states are isoenergetic, while the triplet and quintet states are isoenergetic for tetracations of the same length. Analysis of the geometry reveals three separated polarons for the doublet and quartet states of tricationic n‐oligomers, even though that of the former state has been attributed to a heavy spin contamination. In contrast, the structure of tetracations shows double bipolaron character for the singlet state and two polaron pairs for both the triplet and quintet states. Analyses of both charge and spin density distributions support the polaronic or bipolaronic behavior predicted by molecular geometry for the different electronic states. Results have been also used to evaluate the ionization potentials and the π‐π^* lowest transition energy of infinite polymer chains. Copyright © 2014 John Wiley & Sons, Ltd.     

Computational studies of the interactions between emeraldine and palladium atom

The structural end electronic properties of emeraldine base (EB) dimers interacting with a single Pd atom is investigated within Hartree-Fock with 6-31g(d, p) basis set for non-metal atoms, and 3-21g for Pd. It was found that Pd⁰ might create a stable complex with EB fragments. The influence of the Pd presence on the electronic structure of EB dimers is examined through an analysis of the total density of states and the crystal orbital overlap population (COOP).     

On the initiation of chemical reactions by electronic excitations in molecular solids

In this article we briefly review the results of theoretical simulations for the initiation of chemistry processes in high-explosive crystals from a solid-state-physics viewpoint. We analyze the possibility of initiation of chemical reactions from excited electronic states. In other words, we look for conditions that facilitate electronic excitations in the crystal. Specifically, we describe modifications to the electronic structure of RDX (cyclotrimethylene trinitramine) induced by lattice defects and by a shock wave traversing the solid. Our approach is based on ab initio Hartree–Fock band-structure calculations with electronic correlation corrections. An excitonic mechanism and a hole model, suggested earlier, are discussed in connection with the most recent experimental and theoretical advances in ultrafast optical techniques. We also consider here possible new avenues in the development of detonation theory. Received: 3 December 2001 / Accepted: 9 July 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +1-301/744-4451, E-mail: KuklaMM@ih.navy.mil     

Sn/Ge(1 1 1) α-phase: characterization of image resonances by specular electron reflection and selective electron scattering

Image potential resonances on the Sn/Ge(1 1 1) α-phase are investigated by two closely related methods: specular electron reflection and so-called selective electron scattering. Electrons from image resonances are detected on this surface at 120 and 300 K, i.e. below and above the phase transition at about 200 K. The dispersion of the image resonances reveals at these two temperatures equivalent effective electron masses, which are characteristic for this type of electronic surface states. The results of the two methods are consistent according to the similarity of the scattering processes. Changes in the loss peak intensity with the annealing temperature are assigned to the surface quality and are reflected by characteristic photoemission intensities.     

气相钌原子与氮分子作用机理计算研究

运用B3LYP/6-311+G*(LANL2DZ)详细地研究了Ru原子与N_2分子相互作用的单端位直线型L-Ru N_2和单侧双配位S-Ru N_2及插入化合物NRu N弯曲型和直线型的不同自旋多重度下多个电子态的平衡几何结构、电子结构、轨道布居和振动光谱等性质,同时对构型转化和插入反应过渡态及反应的势能曲线进行了计算.结果表明两种构型的复合物中一般低能态Ru对N_2的活化都不大,直线型的3Δ和3∑-相对基态反应物是能稳定存在的,轨道作用机制是σ/π授予与反馈.化合物NRu N与实验对照,13B1和11A1态可能是实验所观察的,两种构型中众多电子态相对于Ru(a~5F)+2N(~4S)是稳定的.势能曲线体现插入反应能垒很高,生成NRu N化合物在热力学和动力学上都是不利的.     

气相钌原子与氮分子作用机理计算研究

运用B3LYP/6-311+G*(LANL2DZ)详细地研究了Ru原子与N2分子相互作用的单端位直线型L-RuN2和单侧双配位S-RuN2及插入化合物NRuN弯曲型和直线型的不同自旋多重度下多个电子态的平衡几何结构、电子结构、轨道布居和振动光谱等性质，同时对构型转化和插入反应过渡态及反应的势能曲线进行了计算. 结果表明两种构型的复合物中一般低能态Ru对N2的活化都不大，直线型的3和3-相对基态反应物是能稳定存在的，轨道作用机制是授予与反馈. 化合物NRuN与实验对照，13B1和11A1态可能是实验所观察的，两种构型中众多电子态相对于Ru(a5F)+2N(4S)是稳定的. 势能曲线体现插入反应能垒很高，生成NRuN化合物在热力学和动力学上都是不利的.     

Nanocluster dynamics by mutual grazing with overthermal velocities

A theoretical model of the interaction of two molecules during their mutual grazing is developed. Both molecules in the model are considered to be constructed of identical regular chain-like substructures of diatomic fragments. It is shown that at mutual grazing velocities lower than the Bohr speed in these fragments, which serve as IR radiation antennas, simultaneously with the grazing (～10^?12 s) both excitation and the accumulation of low-energy collective vibrational states (eximoles) occur. Energy transport occurs from antennas to trap-bonds in the same molecules and the energy exchange between molecules leads to their simultaneous fragmentation. The probability functions of the considered processes are derived and investigated.     

Trends in adsorption of open-shell atoms and small molecular fragments on the Ag(1 1 1) surface

The chemisorption of various atoms (C, N, O, Cl) and molecular fragments (OH, NH, CH, NH₂, CH₂) on the Ag(1 1 1) surface has been studied by employing the embedded cluster and multireference single- and double-excitation configuration interaction (MRD-CI) methods. Ground and excited states of the cluster-adsorbate systems have been computed and molecular orbitals (MOs) as well as electronic charge density distributions and Mulliken populations have been analyzed in order to extract general trends in chemisorption properties for different adsorbates. It has been found that the adsorbate-surface bond is energetically most favorable when a maximum of two electrons of the metal are shared with a given adsorbate. As a result atomic/molecular fragments with less than six valence electrons (N, CH, C) retain some open shells upon adsorption, whereas oxygen as well as chlorine isovalent species form a singlet ground state on the surface. All species considered except for Cl have mainly covalent bonding character to the surface, with an electronic charge of up to 1.0 transferred to the adsorbate from the silver cluster. It has been shown that the ionicity of the bond is strongly correlated with the electron affinity of the adsorbed species. Binding energies, equilibrium geometry and adsorbate location on the cluster have been computed and compared with available experimental data. In addition, the characteristic properties of chemisorption on Ag(1 1 1) and Pt(1 1 1) surfaces have been compared.     

原子内壳层双光子衰变的相对论效应和屏蔽效应

本文系统地计算了H原子,类H-Xe离子及Xe原子内壳层的双光子衰变速率。阐明其相对论效应和电子屏蔽效应。并与最新的实验结果和他人的理论计算结果进行了比较和分析讨论。 关键词：     

Angular distributions for (3,4)(Lambda)H bound states in the (3,4)He(e,e(')K+) reaction

The (3,4)(Lambda)H and (4)(Lambda)H hypernuclear bound states have been observed for the first time in kaon electroproduction on (3,4)He targets. The production cross sections have been determined at Q(2)=0.35 GeV2 and W=1.91 GeV. For either hypernucleus the nuclear form factor is determined by comparing the angular distribution of the (3,4)He(e,e(')K+)(3,4)(Lambda)H processes to the elementary cross section 1H(e,e K+)Lambda on the free proton, measured during the same experiment.     

Semiempirical valence bond potential energy surfaces for simple chemical reactions: 1 A′ states of H2O and H2F+

A semiemprical valence bond method is employed to study the potential energy surfaces (PESs) of the lowest ¹ A′ states of H₂O and isoelectronic H₂F⁺. The calculation is based on the search for the electronic configurations which play the most important rôle in the formation of the stable electronic states of the molecules and the relevant diatomic fragments. Several approximations are used to reduce the number of permutations in the calculation of the energy matrix. The Moffit atoms-in-molecule approximation is used to correct for the atomic errors arising from the poor basis set. The computed data for the lowest electronic states of OH, HF, HF⁺, H₂O and H₂F⁺, as well as the general behaviour of the PESs for different molecular geometries, are in good agreement with the available ab initio and experimental data.     

β-SiC(001)-(2×1)表面结构的第一性原理研究

利用缀加平面波加局域轨道(APW+LO)的第一性原理方法计算了β-SiC(001)-(2×1)表面的原子及电子结构. 原子结构的计算结果表明，与Si(001)-(2×1) 表面的非对称性Si二聚体模型不同，β-SiC(001)-(2×1)表面为对称性的Si二聚体模型，其二聚体的Si原子间键长也较大，为0.269nm. 电子结构的计算结果表明，在费米能级处有明显的态密度，因此β-SiC(001)-(2×1)表面呈金属性. 在带隙附近存在四个表面态带,其中的两个占有表面态带已由价带的同步辐射光电子能谱实验得到证实. 关键词： 碳化硅 缀加平面波加局域轨道方法 原子结构 电子结构     

Internal Conversion Process of Chlorophyll a in Solvents in Femtosecond Pump-Probe Laser Fields

采用约化密度矩阵理论研究了溶液中叶绿素a分子的内转换过程. 内转换时间可以通过模拟实验荧光亏蚀光谱得到. 计算得到的叶绿素a分子在乙酸乙酯、四氢呋喃和二甲基甲酰胺溶剂中的内转换时间分别是141、147和241 fs. 理论分析表明：荧光亏蚀光谱曲线的振荡行为主要是由分子布居在耦合势能面间的振荡引起的. 分析了两个电子态之间非绝热耦合对内转换时间及荧光亏蚀光谱的影响,还讨论了叶绿素a分子与溶液耦合作用对内转换时间的影响.