Quantum Confinement of the Covalent Bond beyond the Born–Oppenheimer Approximation

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...

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Bibliographic Details
Published in:	The journal of physical chemistry. B 2013-06, Vol.117 (24), p.7270-7276
Main Authors:	Sarsa, A, Alcaraz-Pelegrina, J. M, Le Sech, C, Cruz, S. A
Format:	Article
Language:	eng
Subjects:	Atomic and molecular physics Bonding Born-Oppenheimer approximation Compressing Confinement Covalent bonds Dirichlet problem Exact sciences and technology Molecular properties and interactions with photons Monte Carlo Method Physics Properties of molecules and molecular ions Quantum confinement Quantum Theory Surface Properties Symmetry
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Summary:	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.
ISSN:	1520-6106 1520-5207