On obtaining localized bonding schemes from delocalized molecular-orbital wave functions
On obtaining localized bonding schemes from delocalized molecular-orbital wave functions
复制标题
从离域分子轨道波函数获得局域键合方案
DOI：
10.1007/s002140050225
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发表时间：
1997
影响因子：
1.7
通讯作者：
V. Bachler
中科院分区：
文献类型：
--
作者：
V. Bachler
本文提出了一种简单的方法，将分子轨道的行列式波函数展开成一组由定域在分子原子上的原子轨道组成的行列式波函数。利用这种方法，可以从计算出的分子轨道波函数导出分子的原子轨道行列式及其权重。该程序允许解释的分子轨道行列式波函数的键合方案有关的经典共振结构的有机化学家。利用非限制性分子轨道行列式，得到了丁二烯、丁二烯自由基阳离子和丙烯腈自由基阴离子的成键图式及其键重。它们的主要成键模式与这些分子的相关共振结构雅阁。对于丁二烯自由基阳离子和丙烯腈阴离子，它们被证明是相容的丁二烯和丙烯腈的电化学耦合反应的公认的机制。
A straightforward procedure is proposed for expanding a molecular orbital determinantal wave function into a set of determinantal wave functions composed of atomic orbitals localized at the atoms of a molecule. By employing this method, atomic orbital determinants and their weights can be derived for a molecule from the computed molecular-orbital wave function. The procedure permits the interpretation of a molecular orbital determinantal wave function in terms of bonding schemes related to the classic resonance structures used by organic chemists. By using the unrestricted molecular orbital determinant, bonding schemes and their weights are obtained for butadiene, the butadiene radical cation and the acrylonitrile radical anion. Their dominant bonding schemes are in accord with the relevant resonance structures for these molecules. For the butadiene radical cation and the acrylonitrile anion they are shown to be compatible with the accepted mechanisms of the electrochemical coupling reactions of butadiene and acrylonitrile.