Analysis of covalent bonding by nonergodic Thomas–Fermi theory

It is proposed that covalent bonding can be understood as due to dynamical constraints on electronic motion in atoms which are partially relaxed upon molecule formation. The corresponding delocalization of electronic motion and settling of the electron density stabilizes the molecule. A preliminary implementation of the analysis is based on a form of Thomas–Fermi theory extended so as to account for dynamical constraints leading to a nonergodic population of phase space. Simple estimates for light atoms indicate that nonergodic effects in atoms correspond to large amounts of energy only partially released upon molecule formation due to a variety of antibonding mechanisms.