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首页> 外文期刊>International Journal of Quantum Chemistry >Unraveling Reaction Mechanisms by Means of Quantum Chemical Topology Analysis
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Unraveling Reaction Mechanisms by Means of Quantum Chemical Topology Analysis

机译:通过量子化学拓扑分析揭示反应机理

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A chemical reaction can be understood in terms of geometrical changes of the molecular structures and reordering of the electronic densities involved in the process; therefore, identifying structural and electronic density changes taking place along the reaction coordinate renders valuable information on reaction mechanism. Understanding the atomic rearrangements that occur during chemical reactions is of great importance, and this perspective aims to highlight the major developments in quantum chemical topology analysis, based on the combination of electron localization function and catastrophe theory as useful tools in elucidating the bonding and reactivity patterns of molecules. It reveals all the expected, but still ambiguous, elements of electronic structure extensively used by chemists. The chemical bonds determine chemical reactivity, and this technique offers the possibility of their visualization, allowing chemists to understand how atoms bond, how and where bonds are broken/ formed along a given reaction pathway at a most fundamental level, and so, better following and understanding the changes in the bond pattern. Their results clearly herald a new era, in which the atomic imaging of chemical bonds will constitute a new method for examining chemical structures and reaction mechanisms. The important feature of this procedure is that in practice the scope of its values is systemindependent. In addition, from a practical point of view, it is cheap to calculate and implement because wave functions are the required input, which are easily available from standard calculations. To capture these results two reaction mechanisms: isomerization of C(BH)_2 carbene and the thermal cycloheptatriene-norcaradiene isomerizations have been selected, indicating both the generality and utility of this type of analysis.
机译:可以根据分子结构的几何变化和过程中涉及的电子密度的重排来理解化学反应。因此,识别沿反应坐标发生的结构和电子密度变化可提供有关反应机理的有价值的信息。了解化学反应过程中发生的原子重排非常重要,该观点旨在突出量子化学拓扑分析的主要进展,其基于电子定位功能和突变理论的结合,作为阐明键合和反应性模式的有用工具分子。它揭示了化学家广泛使用的所有预期但仍不明确的电子结构元素。化学键决定化学反应性,这项技术提供了可视化的可能性,使化学家能够了解原子如何键合,如何在最基本的水平上沿着给定的反应路径断裂/形成键,以及因此而更好地遵循和了解债券模式的变化。他们的结果清楚地预示着一个新时代,在这个时代中,化学键的原子成像将构成检查化学结构和反应机理的新方法。此过程的重要特征是在实践中其值的范围与系统无关。另外,从实际的角度来看,由于波动函数是必需的输入,因此计算和实现起来很便宜,这可以从标准计算中轻松获得。为获得这些结果,选择了两种反应机理:C(BH)_2卡宾的异构化和热环庚三烯-降冰片烯的异构化,这表明此类分析的一般性和实用性。

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