NATURAL HYBRID ORBITALS
NATURAL HYBRID ORBITALS
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DOI：
10.1021/ja00544a007
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发表时间：
1980-01-01
影响因子：
15
通讯作者：
WEINHOLD, F
中科院分区：
文献类型：
--
作者：
FOSTER, JP;WEINHOLD, F
根据(精确或近似)一阶密度矩阵中包含的信息，我们描述了一种提取给定分子的一组唯一的原子杂化和键轨道的方法，从而以先验的方式构造其“Lewis结构”。这些天然杂交物在某种意义上是最优的，经过有效的计算，似乎与化学直觉(例如，本特规则中总结的那样)和通过其他程序获得的杂交物很好地吻合。利用简单的INDO-SCF-MO波函数，我们给出了自然杂化轨道分析对表现出各种成键特征的分子的应用，包括单键对、多键、应变环和“弯曲键”、多共振结构、氢键和三中心键。更详细地描述了三个例子：(I)氨伞反转过程中的“轨道跟随”，(Ii)水分子的二聚化，以及(Iii)二硼烷的氢桥键。
From the information contained in the (exact or approximate) first-order density matrix, we describe a method for extracting a unique set of atomic hybrids and bond orbitals for a given molecule, thereby constructing its “Lewis structure” in an a priori manner. These natural hybrids are optimal in a certain sense, are efficiently computed, and seem to agree well with chemical intuition (as summarized, for example, in Bent’s Rule) and with hybrids obtained by other procedures. Using simple INDO-SCF-MO wave functions, we give applications of the naturalhybrid orbital analysis to molecules exhibiting a variety of bonding features, including lone pairs, multiple bonds, strained rings, and “bent bonds”, multiple resonance structures, hydrogen bonds, and three-center bonds. Three examples are described in greater detail:(i)“orbital following” duringammonia umbrella inversion,(ii) the dimerizationof water molecules, and (iii) the hydrogen-bridged bonds of diborane.