Reference Work Entry

Handbook of Computational Chemistry

pp 13-54

Date:

The Position of the Clamped Nuclei Electronic Hamiltonian in Quantum Mechanics

  • Brian SutcliffeAffiliated withService de Chimie Quantique et Photophysique, Université Libre de Bruxelles
  • , R. Guy WoolleyAffiliated withService de Chimie Quantique et Photophysique, Université Libre de Bruxelles

Abstract

Arguments are advanced to support the view that at present it is not possible to derive molecular structure from the full quantum mechanical Coulomb Hamiltonian associated with a given molecular formula that is customarily regarded as representing the molecule in terms of its constituent electrons and nuclei. However molecular structure may be identified provided that some additional chemically motivated assumptions that lead to the clamped nuclei Hamiltonian are added to the quantum mechanical account.