Sutcliffe Brian T, Woolley R Guy
Department of Theoretical Chemistry, Eötvös Loránd University, 112 PO Box 32, H-1518 Budapest, Hungary.
Phys Chem Chem Phys. 2005 Nov 7;7(21):3664-76. doi: 10.1039/b509723c. Epub 2005 Aug 23.
A number of recent papers have considered ways in which molecular structure may be calculated when both the electrons and the nuclei are treated from the outset as quantum particles. This is in contrast to the conventional approach in which the nuclei initially have their positions fixed and so merely provide a potential for electronic motion. The usual approach is generally assumed to be justified by the 1927 work of Born and Oppenheimer. In this paper we discuss what precisely might be anticipated in the way of molecular structure from a mathematical consideration of the spectral properties of the full Coulomb Hamiltonian, to what extent the very idea of molecular structure might be dependent upon treating the nuclei simply as providing a potential and the extent to which the work of Born and Oppenheimer can be used to support this position.
最近有一些论文探讨了从一开始就将电子和原子核都视为量子粒子时，分子结构的计算方法。这与传统方法形成对比，在传统方法中，原子核最初位置固定，仅为电子运动提供一个势场。通常认为，这种常规方法是由玻恩（Born）和奥本海默（Oppenheimer）1927年的工作所证明的。在本文中，我们将从全库仑哈密顿量的光谱特性的数学考虑出发，讨论在分子结构方面究竟可以预期到什么，分子结构的概念在多大程度上可能依赖于将原子核仅仅视为提供一个势场，以及玻恩和奥本海默的工作在多大程度上可以用来支持这一观点。
