Collect. Czech. Chem. Commun. 2007, 72, 252-268

The Quantum Mechanics of Cohesion

Roy McWeeny

Dipartimento di Chimica e Chimica Industriale, Via Risorgimento 35, 56100 Pisa, Italy


We consider the fundamental problem of "what makes atoms stick together in molecules, crystals, or clusters?" The Heitler and London paper (1927) on the hydrogen molecule marked a first attempt to discuss, in terms of quantum mechanics, the interaction of two atoms with unpaired spins. The aim of this note is to show how the primitive concepts used eighty years ago still retain a certain validity even in a much more general context. We consider in fact the interaction of two arbitrary systems, each with a resultant spin angular momentum, and show how the interaction energy depends on the scalar product of the two resultants. The actual nature of the two systems is irrelevant: they may be atoms, molecules, or ionic species of any kind each described by a wave function which may be, in principle, exact. This provides a first step in the formulation of any general theory of cohesion.

Keywords: Cohesion; Intermolecular interaction; Electron density; Density matrix; Spin coupling; Hamiltonian; Quantum chemistry.

References: 11 live references.