共查询到19条相似文献,搜索用时 48 毫秒
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用分子图形软件设计出49种硫原子团簇Sn+(n=3~13)的结构,使用B3LYP密度泛函进行几何构型优化和振动频率计算,根据分子的总能量得出最稳定的同分异构体.在硫原子团簇正离子中,大部分原子为二配位成键.带有一、三配位的原子结构的总能量较高.部分最稳定硫原子团簇正离子的构型与最稳定的中性硫原子团簇的构型完全不同. 相似文献
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激光溅射下原子团簇生长的非平衡动力学 总被引:3,自引:1,他引:2
以激光溅射的方式,可以产生不同尺寸与组分的原子团簇.但是对这些团簇的生长过程,却一直缺少比较深入和细致的研究.本文结合激光真空溅射石墨的实验条件,考虑了激光能量、体系膨胀、环境压力、热量辐射等诸多因素,建立了在该条件下碳原子团簇生长的物理模型,得出了相应的动力学方程的数值解.计算结果表明:每个激光脉冲溅射出约8×10-9mol(5×1015个)粒子,它们产生时的初始压力约为2×105Pa.由于扩散等因素,团簇的形成反应在785μs后已不可能进行,但是各团簇产物的产率在反应开始后0.4μs左右已达到最大值,在约1.5μs内反应即已基本完成,因为此后原子团簇的尺寸分布不再有显著的差异. 相似文献
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用分子图形学方法设计出26种P10模型,并对其进行了分子力学、PM3半经验量子化学和Hartree-Fock从头算优化。在P10原子团簇模型设计中,磷原子采用一、二、三或四配位。大部分P10的模型是在P9+和P8的模型上分别增加1、2个原子生成的。这些模型包括15种在势能面上局域极小点和11种鞍点(或过渡态)。从模型优化后的能量比较可知,2个四面体P4与1个P2通过4个单键连接的桥式结构最稳定。从最稳定楔状P8可以派生多种构型,其中有一种的能量也相当低。由正四面体P4和楔状P8派生出的结构具有能量优势,它们是构造大分子磷原子团簇的重要的结构基元。在模型几何优化中,得到了带有2个一配位原子的特殊结构,它含有2个三键(1.95A)。 相似文献
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以激光溅射的方式,可以产生不同尺寸与组分的原子团簇.但是对这些团簇的生长过程,却一直缺少比较深入和细致的研究.本文结合激光真空溅射石墨的实验条件,考虑了激光能量、体系膨胀、环境压力、热量辐射等诸多因素,建立了在该条件下碳原子团簇生长的物理模型,得出了相应的动力学方程的数值解.计算结果表明:每个激光脉冲溅射出约8×10-9mol(5×1015个)粒子,它们产生时的初始压力约为2×105Pa.由于扩散等因素,团簇的形成反应在7.85μs后已不可能进行,但是各团簇产物的产率在反应开始后0.4μs左右已达到最大值,在约1.5μs内反应即已基本完成,因为此后原子团簇的尺寸分布不再有显著的差异. 相似文献
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探索非贵金属材料作为高效氧还原反应催化剂是迫切需要的,但具有一定的挑战性。本文采用等离子体轰击和酸洗相结合的策略合成了Co原子团簇修饰的多孔碳载体催化剂(CoAC/NC)。通过多种表征手段证实了的原子团簇特征。所得到的CoAC/NC催化剂在三电极体系和锌-空电池方面都表现出优异的氧还原反应活性。该催化剂的氧还原反应半波电位为0.887 V,显著优于商业Pt/C催化剂,且表现出优异的稳定性。此外,该催化剂组装的锌-空电池的峰值功率密度为181.5 mW∙cm−2,同样远高于Pt/C催化剂。这项工作不仅合成了一种高效的氧还原反应催化剂,而且为原子团簇催化剂的理性设计和实际应用提供了新的见解。 相似文献
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自由表面的Ni原子团簇的熔化 总被引:3,自引:0,他引:3
采用分子动力学模拟技术研究了不同尺寸的Ni原子团簇的熔化过程.团簇的最初构型为FCC结构.研究结果表明,原子团簇的熔化温度与原子团簇中原子的个数有关,团簇的熔化首先从表面开始,当外层原子成为液态后,整个团簇的熔化从液态层开始,直至核心区域.该熔化过程可以被称为非均质熔化,自由表面充当非均质形核位置.作为对比,对无自由表面的大块固态Ni的熔化过程也进行了模拟,其熔化温度高于实验温度约400 K.表明对无自由表面的大块固态的熔化过程,液相形成无非均质形核位置,熔化的本质过程受均质形核机理控制. 相似文献
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The interactions between AgnO-(n=1-8) and H2 (or D2) were explored by combination of the mass spectroscopy experiments and density function theory (DFT) calculations. The experiments found that all oxygen atoms in AgnO-(n=1-8) are inert in the interactions with H2 or D2 at the low temperature of 150 K, which is in contrast to their high reactivity with CO under the same condition. These observations are parallel with the preferential oxidation (PROX) of CO in excess hydrogen catalyzed by dispersed silver species in the condensed phase. Possible reaction paths between AgnO-(n=1-8) and H2 were explored using DFT calculations. The results indicated that adsorption of H2 on any site of AgnO-(n=1-8) is extremely weak, and oxidation of H2 by any kind of oxygen in AgnO-(n=1-8) has an apparent barrier strongly dependent on the adsorption style of the "O". These experiments and theoretical results about cluster reactions provided molecule-level insights into the activity of atomic oxygen on real silver catalysts. 相似文献
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Designing principles for forming stable metallic clusters whose chemistry mimics different atoms of the periodic table are discussed. It is shown that while bulk Al is a metal, the chemistry of an Al13 resembles that of a halogen atom, a CAl12 resembles an inert atom, while a NAl12 resembles an alkali atom. The feasibility of making new materials using clusters as the building blocks is discussed. An ionic solid made out of Al13 (or BAl12) and Cs is shown to be metastable and marked by a large gap at the Fermi energy even though bulk Al and Cs are metals. 相似文献
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原子吸收,原子荧光和火焰光谱分析 总被引:2,自引:0,他引:2
本文根据1988~1990年国内主要分析刊物所发表的文章,以及第三届北京分析测试学术报告会及展览会(BCEIA)、中国化学会第三届原子光谱会的主要论文,对我国原子吸收、原子荧光和火焰光谱分析的进展进行了评述,对于国外有关的重要文章也简单地加以介绍。 相似文献
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The stability and diffusion behaviors of 1.3 MPa Pt, Pd, Ni and Cu clusters supported on Pd(001) surface were studied by the Monte Carlo method. The support surface can strongly influence the stability and diffusion behaviors of the supported clusters. The structure transition temperatures of the supported clusters are much lower than the melting temperatures of their corresponding free clusters due to the vibration coupling between the support and the clusters. The stability of the supported clusters depends on not only the strength of metal support interaction but also the strength of the metal metal interaction. The diffusion constants of supported 1.3 MPa clusters are similar to those of corresponding metal atoms. Combining the diffusion parameters with the critical temperature of the supported clusters, the thermal stability is closely related to the diffusion behaviors of the metal clusters. 相似文献
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Geoffrey A. Ozin Steven A. Mitchell 《Angewandte Chemie (International ed. in English)》1983,22(9):674-694
Recent advances in the synthesis and spectroscopic characterization of ligand-free metal clusters immobilized in cryogenic rare gas matrices have contributed greatly to the understanding of electronic, geometric, dynamic, and chemical bonding properties of a wide range of uni- and bimetallic clusters as a function of nuclearity and metal type. The knowledge accumulated on molecular metal aggregates devoid of ligands and isolated on various supports will form an important data base for gauging the reliability of quantum chemical calculations on metal clusters, as well as for comprehending certain aspects of chemisorption on, and catalysis by, supported metal clusters. It can be envisaged that information on ligand-free metal clusters entrapped in a wide range of matrix environments in conjunction with the data for these same metal clusters in the gas phase and in molecular beams will probably contribute towards understanding metal-support interactions and to the designed synthesis of a new breed of high-technology heterogeneous catalysts in the not too distant future. 相似文献