Molecular structure calculations without clamping the nuclei.
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.
Sutcliffe
Brian T
BT
Department of Theoretical Chemistry, Eötvös Loránd University, 112 PO Box 32, H-1518 Budapest, Hungary. bsutclif@ulb.ac.be
Woolley
R Guy
RG
D000465:Algorithms; D003198:Computer Simulation; D019471:Elementary Particle Interactions; D004601:Elementary Particles; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D011789:Quantum Theory; D055672:Static Electricity