Pendás A Martín, Francisco Evelio, Blanco Miguel A, Gatti Carlo
Departamento de Química Física y Analítica, Facultad de Química, Universidad de Oviedo, 33006, Oviedo, Spain.
Chemistry. 2007;13(33):9362-71. doi: 10.1002/chem.200700408.
Evidence that the bond paths of the quantum theory of atoms-in-molecules (QTAIM) signal preferred quantum-mechanical exchange channels is presented. We show how bond paths between an atom A and the atoms B in its environment appear to be determined by competition among the A-B exchange-correlation energies that always contribute to stabilize the A-B interactions. These pairwise additive stabilizations depend neither on the attractive or repulsive nature of the classical electrostatic interaction between the atoms' charge densities, nor on the change in the self energies of the atoms involved. These other terms may well cause an overall molecular-energy increase in spite of a possibly large A-B exchange-correlation stabilization. After our proposal, bond paths, both at and out of equilibrium geometries, are endowed with a specific energetic meaning that should contribute to reconcile the orthodox QTAIM interpretation with other widely accepted views, and to settle recent controversies questioning the meaning of hydrogen-hydrogen bonding and the nature of the so-called "steric interactions", the role of bond paths in endohedral complexes, and the generality of the results provided by the QTAIM. Implications for the nature of more general closed-shell interactions are also briefly discussed.
本文给出了分子中原子量子理论（QTAIM）的键径表明优先量子力学交换通道的证据。我们展示了原子A与其环境中的原子B之间的键径似乎是如何由A - B交换相关能量之间的竞争所决定的，这些能量总是有助于稳定A - B相互作用。这些成对相加的稳定作用既不取决于原子电荷密度之间经典静电相互作用的吸引或排斥性质，也不取决于所涉及原子自能的变化。尽管A - B交换相关稳定作用可能很大，但这些其他项很可能导致分子总能量增加。在我们提出建议之后，平衡几何构型处和非平衡几何构型处的键径都具有特定的能量意义，这应该有助于使正统的QTAIM解释与其他广泛接受的观点相协调，并解决最近关于氢 - 氢键的意义、所谓“立体相互作用”的性质、键径在内嵌配合物中的作用以及QTAIM提供的结果的普遍性的争议。还简要讨论了对更一般闭壳层相互作用性质的影响。
