Ab initio through‐space/bond interaction analysis of the long C–C bonds in Bi(anthracene‐9,10‐dimethylene) photoisomers
Ab initio through‐space/bond interaction analysis of the long C–C bonds in Bi(anthracene‐9,10‐dimethylene) photoisomers
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Bi(蒽-9,10-二亚甲基)光异构体中长C-C键的从头算通过空间/键相互作用分析
DOI：
10.1002/qua.1104
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发表时间：
2002
影响因子：
2.2
通讯作者：
Y. Aoki
中科院分区：
文献类型：
--
作者：
Y. Orimoto;Y. Aoki
双（蒽-9，10-二亚甲基）光异构体具有非常长的C-C单键。为了研究C-C键的延长，我们提出了一种在从头算分子轨道方法水平上定量分析分子中轨道相互作用的新方法。在这个过程中，我们可以通过人为增加高斯函数中指数的绝对值来切断分子中特定的空间/键相互作用。然后，空间轨道相互作用被完美地切断，并且，构成总能量的每一项，即，核-电子吸引力，电子-电子排斥力，以及核-核排斥力相互抵消。用这种方法分析了几种光异构体的模型分子。发现苯环上的p轨道和C-C键上的σ* 轨道之间的轨道相互作用，即σσ* 电子通过π轨道转移，当这些轨道处于“周面”构象时，有效地削弱了C-C键。John Wiley & Sons，Inc.国际量子化学杂志，2001年
The bi(anthracene-9,10-dimethylene) photoisomer has remarkably long C–C single bonds. To examine the lengthening of the C–C bond, we propose a novel procedure for quantitatively analyzing orbital interactions in a molecule at the level of the ab initio molecular orbital method. In this procedure, we can cut off the specific through-space/bond interactions in a molecule by artificially increasing the absolute magnitude of the exponents in a Gaussian function. Then, the spatial orbital interactions were perfectly cut off, and, each term that makes up the total energy, that is, the nuclear–electron attractions, the electron–electron repulsions, and the nuclear–nuclear repulsions cancel each other. Several model molecules of the photoisomer were analyzed by this procedure. It was found that the orbital interaction between the p orbital on the benzene ring and the σ* orbital on the C–C bond in question, σσ* electron transfer through π orbital, weakens the C–C bond efficiently when these orbitals were located in the “periplanar” conformation. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001