Quantum confinement of the covalent bond beyond the Born-Oppenheimer approximation

J Phys Chem B. 2013 Jun 20;117(24):7270-6. doi: 10.1021/jp402727b. Epub 2013 Jun 11.

Abstract

Dirichlet boundary conditions with different symmetries, spherical and cylindrical impenetrable surfaces, are imposed on the covalent electron pair of a molecular bond. Accurate results for different observable like energy and interparticle distances are calculated using quantum Monte Carlo methods beyond the Born-Oppenheimer approximation. The spherical confinement induces a raise in the bond energy and shortens the internuclear distances even for a relatively soft confinement. When cylindrical symmetry is considered, similar qualitative behavior is observed though only the electrons are confined. A compression followed by a relaxation process of the confined bond is shown to induce a vibrationally excited state. Finally, a brief qualitative discussion based on a simplified picture of the role of compression/relaxation cycles in enzyme catalysis is given.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Monte Carlo Method
  • Quantum Theory*
  • Surface Properties