分子轨道成分计算.pdfVIP

2011 年第 69 卷 化 学 学 报 Vol. 69, 2011 第 20 期, 2393～2406 ACTA CHIMICA SINICA No. 20, 2393～2406 ·研究论文· 分子轨道成分的计算 卢 天 陈飞武* (北京科技大学化学与生物工程学院 北京 100083) 摘要 量子化学文献中经常涉及到“分子轨道成分”概 , 然而相应的计算方法却没有普遍得到重视, 甚至存在严重误 区. 本工作专门对分子轨道中基函数的成分、原子轨道的成分以及原子的成分这些基本概念和计算方法进行了详细讨论, 通过实例分析比较了不同方法间的差异, 同时指出了计算和分析时需要注意的问题, 给出了在方法选择上的建议. 关键词 轨道成分; 基函数; 原子轨道; 分子环境中的原子轨道; 自然原子轨道 Calculation of Molecular Orbital Composition Lu, Tian Chen, Feiwu* (School of Chemical and Biological Engineering, University of Science and Technology Beijing, Beijing 100083) Abstract The concept of the molecular orbital composition is often involved in quantum chemistry litera- tures. However, no enough emphasis has been placed on the corresponding calculation methods, and even there exist some serious misunderstandings. In this article, the basic concepts and calculation methods of composition of basis functions, atomic orbitals and atoms in molecular orbitals are discussed in detail, the differences between various methods are analyzed and compared with examples, meanwhile, the problems in calculations and analyses that need to be noticed are pointed out, the suggestions for choosing appropriate calculation methods are also given. Keywords orbital composition; basis function; atomic orbital; atomic orbitals in molecular environments; natural atomic orbital 量子化学工作者在分析计算结果时经常会用到“分 问题进行介绍, 之后通过实际计算分析比较不同方法间 子轨道成分”的概念[1～ 17]. 将轨道波函数分解为各个组 的差异, 并给出方法选用的建议, 帮助读者正确地理解 成部分的贡献有助于了解体系内在特点,