AlH分子A’Ⅱ态的发射光谱和势能曲线

本文以傅里叶变换光谱法在0.05cm~(-1)的分辨率上观测了AIH分子A′П-X′∑跃迁的0-0,0-1,0-2,1-1,1-2,1-3六个发射谱带,对它们进行归属,用最小二乘方拟合得出了有关分子常数,进而用RKR方法得出A′П态在平衡构型附近的势函数.再利用谱线的预离解线宽,得出该势能曲线的短程部分和长程部分,并用三次样条函数插值法把这三部分光滑地联接在一起.所得出的A′П态的离解限的激近值D=1900.50cm~(-1)(相对于势能最低点)和无转动态的势能曲线的势垒高度H=327.57cm~(-1).     

铝氢化物(AlHn)(n=1-6)团簇结构与光谱的研究

采用密度泛函(DFT)中的B3P86方法，在Dunning的相关一致基组cc-PVTZ水平上，对铝氢化物(AlHn)(n=1-6)团簇的可能几何构型进行优化计算，得出最稳定构型的几何参数、电子结构、振动频率和光谱等性质参数，并给出了最稳定结构的总能量(ET)、结合能(EBT)、平均结合能(Eav)、电离势(EIP)、能隙(Eg)、费米能级(EF)和氢原子差分吸附能(Ediff)等．结果表明铝氢化物团簇基态稳定结构的电子态分别为：n为奇数为单重态 和 ，n为偶数为双重态 和 ；由于Al原子属于缺电子原子，能与等电子原子H化合，通过氢桥键形成氢化物，本文优化计算发现，铝氢化物团簇最稳定的构型都存在氢桥键，且n为奇数的氢化物的氢桥键作用比相邻偶数的氢化物强．最后计算了铝氢化物团簇最稳定结构的红外光谱、平均结合能、电离势、能隙和费米能级等动力学电子特性，分析得出(AlHn)(n=1-6)团簇中AlH3的电离势和能隙最大，说明该氢化物最稳定，氢原子差分吸附能最大．     

铝氢化物(AlHn)(n=1-6)团簇结构与光谱的研究

采用密度泛函(DFT)中的B3P86方法,在Dunning的相关一致基组cc-PVTZ水平上,对铝氢化物(AlHn)(n=1-6)团簇的可能几何构型进行优化计算,得出最稳定构型的几何参数、电子结构、振动频率和光谱等性质参数,并给出了最稳定结构的总能量(ET)、结合能(EBT)、平均结合能(Eav)、电离势(EIP)、能隙(Eg)、费米能级(EF)和氢原子差分吸附能(Ediff)等．结果表明铝氢化物团簇基态稳定结构的电子态分别为：n为奇数为单重态 和 ,n为偶数为双重态 和 ;由于Al原子属于缺电子原子,能与等电子原子H化合,通过氢桥键形成氢化物,本文优化计算发现,铝氢化物团簇最稳定的构型都存在氢桥键,且n为奇数的氢化物的氢桥键作用比相邻偶数的氢化物强．最后计算了铝氢化物团簇最稳定结构的红外光谱、平均结合能、电离势、能隙和费米能级等动力学电子特性,分析得出(AlHn)(n=1-6)团簇中AlH3的电离势和能隙最大,说明该氢化物最稳定,氢原子差分吸附能最大．     

AlH(3) and Al(2)H(6): magic clusters with unmagical properties

Enhanced stability, low electron affinity, and high ionization potential are the hallmarks of a "magic" cluster. With an electron affinity of 0.28 eV, ionization potential of 11.43 eV, and a large binding energy, AlH(3) satisfies these criteria. However, unlike other magic clusters that interact only weakly with each other, two AlH(3) clusters bind to each other with an energy of 1.54 eV. The resulting Al(2)H(6), while also a magic cluster in its own right, possesses the most unusual property that the difference between its adiabatic and vertical detachment energy is about 2 eV--the largest of any known cluster. These results, based on density functional theory, are verified experimentally through photodetachment spectroscopy.     

Hyperfine Parameters for Aluminum Hydride: An ab Initio Molecular Orbital Study

An extensive ab initio molecular orbital study of the (27)Al nuclear spin-rotation and nuclear quadrupolar coupling constants in aluminum hydride, AlH, has been performed. The (27)Al nuclear spin-rotation constant (C( perpendicular)), calculated to be approximately 300 kHz, was neglected in a previous analysis of the hyperfine structure in the microwave spectrum (M. Goto and S. Saito, Astrophys. J. 452, L147-148 (1995)). Unfortunately, the ab initio calculations do not provide a definitive value for the aluminum nuclear quadrupolar coupling constant, but suggest a value of -49+/-4 MHz. It is apparent that the microwave study of AlH should be repeated. Copyright 2001 Academic Press.     

31P N.M.R. studies of the gas phase and solvent chemical shifts of phosphorus tribromide

A method is presented for calculating the electric field gradient (EFG) at the nuclei in diatomic molecules from fully numerical wavefunctions. The method is tested on Hartree-Fock-Slater (HFS) wavefunctions. Benchmarks are given for LiH, BH, FH, NaH, AlH and ClH.     

AlH+离子A2∏态势能函数的变分研究简

采用双原子分子离子XY+的能量自洽法(Energy-consistent-method for ion XY+,ECMI)研究了氢化铝离子AlH+激发态A2∏的解析势能函数,并与采用中性双原子分子势能函数Morse势和HuxleyMurrell-Sorbie(HMS)势分析该离子该电子态的势能行为的结果、基于实验的Rydberg-Klein-Ress(RKR)数据和MCSCF方法的理论研究结果进行了比较.结果表明,由ECMI方法得到的解析势能函数ECMI势明显优于Morse势和HMS势的表现及MCSCF方法的结果,与RKR数据符合得很好,并能得到RKR数据缺乏的离解区和渐近区数据以及正确的离解极限,而正确的全程势能数据对研究各种散射问题都是非常必要的.     

Emission spectroscopy of the A<Superscript>1</Superscript>Π–X<Superscript>1</Superscript>Σ<Superscript>+</Superscript> system of AlH

The high-resolution emission spectrum of the A¹ Π–X¹Σ⁺ transition of AlH was observed in the 18 000–25 000 cm^-1 spectral region using a conventional spectroscopic technique. The AlH molecules were excited in an Al hollow-cathode lamp filled with a mixture of Ne carried gas and a trace amount of NH₃. The emission from the discharge was observed with a plane grating spectrograph and recorded by a photomultiplier tube. In total 163 transition wave numbers belonging to six bands (0-0,1 and 1-0,1,2,3) were precisely measured and rotationally analysed. In the final fit the present data have been combined with available high-resolution measurements of the vibration-rotation bands by White et al. [J. Chem. Phys. 99, 8371 (1993)]. This procedure enabled extracting molecular constants for the A¹ Π and X¹ Σ⁺ states of AlH. A very slight local perturbation has been discovered in the v=1 vibration level of the A¹ Π state at J=5. This was probably caused by the interaction with the a³Π state.     

Quantum chemical calculations on Al-CVD using DMEAA: surface reaction mechanism of AlH3 on Al(111)

An investigation has been made of the elementary surface reactions of alane and its surface dissociation products using density functional theory and a cluster model to elucidate the reaction mechanism of the deposition of aluminium in aluminium chemical vapour deposition (Al-CVD) using dimethylethylamine alane (DMEAA). Molecular structures, potential energies, and normal mode frequencies of the reactants, the products, and the transition states were calculated for each of the surface elementary reactions. Based on transition state theory, rate constants were estimated from the calculation results. The proposed reaction mechanism is the following. DMEAA is adsorbed onto an aluminium surface without any dissociation in the gas phase; DMEAA dissociates into dimethylethylamine (DMEA) and alane on the surface; DMEA is desorbed and alane remains adsorbed; the adsorbed alane molecules dissociate to AlH₂, AlH, and H on the surface; hydrogen molecules to be desorbed are produced from the hydrogen atoms of AlH whose aluminium atoms form a quasi-aluminium surface on the original surface. The cluster size and structure dependence in quantum chemical calculations has also been considered using model clusters.     

Emission bands of AIH (X1Σ+): The 2-0 sequence

Seven bands of the 2-0 sequence of AlH in its X¹Σ⁺ ground state have been observed in emission from a carbon furnace and recorded with a Bomem interferometer. Improved values for the molecular constants have been obtained. The principal constants are B_e = 6.3937(4), α₃ = 0.1868(3), 10⁴D_e = 3.683(10), ω_e = 1682.43, and ω_eχ_e = 29.11 cm⁻¹, where the error limits are 3σ. Possibilities for observing AlH in astrophysical sources are discussed.     

Pressure-induced hydrogen-dominant metallic state in aluminum hydride

Two structural transitions in covalent aluminum hydride AlH3 were characterized at high pressure. A metallic phase stable above 100 GPa is found to have a remarkably simple cubic structure with shortest first-neighbor H-H distances ever measured except in H2 molecule. Although the high-pressure phase is predicted to be superconductive, this was not observed experimentally down to 4 K over the pressure range 120-164 GPa. The results indicate that the superconducting behavior may be more complex than anticipated.     

On the modeling of hydrogen diffusion processes and complex formation in p-type crystalline silicon

Deuterium diffusion profiles in p-type silicon doped with boron (10¹⁷–10¹⁹ cm^-3) and aluminum (10¹⁸ cm^-3) are simulated with an improved version of a previously reported model. The new approach, based on the observation of experimental profiles, excludes H₂ molecule formation and leads to a reduced fit parameters model. The different diffusion coefficients and activation energies of H⁰ and H⁺ species are determined and discussed in the light of available data. The dissociation energies of BH and AlH complexes are also calculated and found to be in good agreement with the corresponding reported values in the literature.     

Simple three-parameter model potential for diatomic systems: from weakly and strongly bound molecules to metastable molecular ions

Based on a simplest molecular-orbital theory of H(2)(+), a three-parameter model potential function is proposed to describe ground-state diatomic systems with closed-shell and/or S-type valence-shell constituents over a significantly wide range of internuclear distances. More than 200 weakly and strongly bound diatomics have been studied, including neutral and singly charged diatomics (e.g., H(2), Li(2), LiH, Cd(2), Na(2)(+), and RbH(-)), long-range bound diatomics (e.g., NaAr, CdNe, He(2), CaHe, SrHe, and BaHe), metastable molecular dications (e.g., BeH(++), AlH(++), Mg(2)(++), and LiBa(++)), and molecular trications (e.g., YHe(+++) and ScHe(+++)).     

BH2和AlH2分子的结构及其解析势能函数

运用二次组态相关(QCISD)方法，分别选用6-311++G(3df,3pd)和D95(3df,3pd)基组，对BH₂和AlH₂分子的结构进行了优化计算，得到BH₂分子的稳态结构为C_2v构型，电子态为²A₁、平衡核间距R_BH=0.1187nm、键角∠HBH=128.791°、离解能D_e=3.65eV、基态振动频率ν₁(a₁)=1020.103cm^-1,ν₂(a₁)=2598.144cm^-1,ν₃(b₂)=2759.304cm^-1.AlH₂分子的稳态结构也为C_2v构型，电子态为²A₁、平衡核间距R_AlH=0.1592nm、键角∠HAlH=118.095°、离解能D_e=2.27eV、基态振动频率ν₁(a₁)=780.81cm^-1,ν₂(a₁)=1880.81cm^-1，ν₃(b₂)=1910.46cm^-1.采用多体项展式理论推导了基态BH₂和AlH₂分子的解析势能函数，其等值势能图准确再现了BH₂和AlH₂分子的结构特征及其势阱深度与位置.分析讨论势能面的静态特征时得到BH+H→BH₂反应中存在鞍点，活化能为150.204kJ/mol；AlH+H→AlH₂反应中也存在鞍点，活化能为54.8064kJ/mol. 关键词： 2')" href="#">BH₂ 2')" href="#">AlH₂ Murrell-Sorbie函数 多体项展式理论 解析势能函数     

The emission spectrum of the CΣ–XΣ system of AlH

The ultraviolet spectrum of AlH has been investigated at high resolution between 42 000 and 45 000 cm⁻¹ using a conventional spectroscopic technique. The AlH molecules were formed and excited in an aluminium hollow-cathode lamp with two anodes, filled with a mixture of Ne carried gas and a trace of NH₃. The emission from the discharge was observed with a plane grating spectrograph and recorded by a photomultiplier tube. The 0–0, 1–1 and 1–2 bands of the C¹Σ⁺–X¹Σ⁺ transition have been identified and rotationally analyzed. The new data were elaborated with help of recent X¹Σ⁺ state parameters reported by White et al. [J. Chem. Phys. 99 (1993) 8371–8378] and by Szajna and Zachwieja [Eur. Phys. J. D. 55 (2009) 549–555]. Determined constants of the excited C¹Σ⁺ state include: T_e = 44 675.3711(57) cm⁻¹, ω_e = 1575.3357(42) cm⁻¹, ω_ex_e = [125.5] cm⁻¹, B_e = 6.66804(32) cm⁻¹, α_e = 0.55839(56) cm⁻¹, D_e = 2.23(13) × 10⁻⁴ cm⁻¹, β_e = 6.13(25) × 10⁻⁴ cm⁻¹ and r_e = 1.613132(39) Å. The C¹Σ⁺ state is found to be extensively perturbed in the v = 0 and 1 vibrational level at J = 20, 22 − 27 and J = 5 − 9, respectively. This was probably caused by the interaction with the vibrational levels of the outer minimum.     

2,2,9,9‐Tetramethylcyclonona‐3,5,7‐trienylidene vs. its heterocyclic analogues: A quest for stable carbenes at DFT

Replacement of α‐methylenes with BH, AlH, CMe₂, SiH₂, NH, NMe, N^tButyl, NPh, PH, O, and S in non‐planar cyclonona‐3,5,7‐trienylidene (CH₂) alters its status from an unstable transition state to rather stable minima, at B3LYP/6‐311++G**//B3LYP/6‐31 + G* levels of theory. All species appear with singlet closed shell (S_cs) global minima, except for SiH₂ and CH₂ which exhibit triplet electronic ground states. The order of stability based on singlet–triplet energy gap (ΔE_s–t / kcalmol^?1) is: CMe₂ (45.8) > NH (35.8) > NMe (32.3) > O (31.5) > N^tButyl (27.7) ≥ NPh (27.5) ≥ BH (27.4) > S (21.9) > PH (17.0) > CH₂ (?4.4) > SiH₂ (?12.5). In contrast to many reports on N‐heterocyclic carbenes, here alkyl groups appear to exert a higher stabilizing effect than heteroatoms, making CMe₂ the most stable. In addition bulky NMe, N^tButyl, and NPh appear more nucleophilic than their synthesized imidazol‐2‐ylidene congeners. Excluding SiH₂, isodesmic reactions reveal that all substituents stabilize singlet state considerably more than the corresponding triplet. Finally, this work is hoped to pave the path for future matrix isolations and IR studies of these rather stable cyclic non‐planar carbenes. Copyright © 2013 John Wiley & Sons, Ltd.     

ORSAT and modifications of SEFT and APT

Up to now, three subspectra are usually needed for the complete assignment of all signals in 13C spectrum: two DEPT spectra (phi = 90 degrees and phi = 135 degrees) and a proton decoupled spectrum. In this paper, we present a method in which a complete assignment becomes possible with merely two spectra. For this purpose, a new pulse sequence (ORSAT) has been elaborated by using off-resonance irradiation. The method described here is a further development of SEFT and APT. The second required spectrum is a DEPT (phi = 135 degrees). Signal assignment of cholesteryl acetate is demonstrated as an example. 13C routine spectroscopy can be significantly accelerated by applying this method.     

Some aspects of nucleation and evolution of microscopic and mesoscopic cracks and quasi-brittle fracture of homogeneous materials

The dynamics of nucleation of microcracks in the region of a developing macroscopic crack has been studied using scanning electron microscopy during in situ experiment and the acoustic emission method. An explosive-like nucleation of microcracks and the influence of dissipative properties of a material on the size and the rate of redistribution of local stresses of the microcracks have been established. Each of nucleations of microscopic and mesoscopic defects is considered as an act of local testing of the dissipative ability of the system, and the interaction between microcracks is determined by relaxation processes when the ability is sufficient. With deteriorating dissipative properties (with increasing residence time under loading, deformation rate, etc.), an elastic linear interaction becomes possible, and the macroscopic fracture occurs. In the microcrack dynamics, a specific ductile-brittle transition is determined by a time deterioration of the dissipative properties of the material under the action of a mechanical load. Generally, as a large latent energy is stored during deformation, a macroscopic fracture can be caused by any little discrete structural transformation.     

Geometry and Elasticity of Strips and Flowers

We solve several problems that involve imposing metrics on surfaces. The problem of a strip with a linear metric gradient is formulated in terms of a Lagrangian similar to those used for spin systems. We are able to show that the low energy state of long strips is a twisted helical state like a telephone cord. We then extend the techniques used in this solution to two–dimensional sheets with more general metrics. We find evolution equations and show that when they are not singular, a surface is determined by knowledge of its metric, and the shape of the surface along one line. Finally, we provide numerical evidence by minimizing a suitable energy functional that once these evolution equations become singular, either the surface is not differentiable, or else the metric deviates from the target metric.     

Membranes and films of zeolite and zeolite-like materials

An ideal structure of zeolite membrane should be a slice of a perfect zeolite crystal attached on a porous metal or ceramic support. To maximize the throughput, the zeolite layer must be very thin, limited only by the cell dimension of zeolite. Separation of a mixture may then be achieved based on the molecular sieving ability of zeolite, which allows only molecules smaller than a critical size to pass through. A variety of methods have been reported for the preparation of zeolite membranes, but so far a perfect epitaxial zeolite layer is still out of reach and only a polycrystalline zeolite membrane can be obtained. The first part of this review focuses on the permeation of gases and vapors through a polycrystalline zeolite membrane as a separation means. The effect of microstructure on permeance will also be discussed, as well as the preparation methods leading to different microstructures. In addition to the usage as a shape-selective membrane, thin films of zeolite and zeolite-like molecular sieves can also serve as hosts for the encapsulation and orientation of guest atoms and molecules and their clusters. In the second part of this review, the production of layers of aligned microporous molecular sieve crystals on supports and the fabrication of supported thin zeolite-like nanoporous silica films as well as their potential applications on the preparation of advanced materials are discussed.