Exclusion principle repulsion effects on the covalent bond beyond the Born–Oppenheimer approximation

Literature Information

Publication Date 2019-04-18
DOI 10.1039/C9CP01063G
Impact Factor 3.676
Authors

A. Sarsa, J. M. Alcaraz-Pelegrina, C. Le Sech


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Abstract

The changes in the covalent bond of the hydrogen molecule limited in space by a spherical hard boundary are studied. The sphere is moved along an axis parallel or orthogonal to the molecular axis. The diffusion Monte Carlo approach is used to solve the Schrödinger equation with the relevant boundary conditions and to evaluate the changes in the bond energy versus the location of the sphere. The vertical and lateral quantum forces exerted on the sphere are evaluated by calculating the energy derivative versus the distances to the sphere. The results show that the quantum forces present an important dependence on the distance and vanish rapidly as the separation between the sphere and the molecule increases. In the limiting case the molecular bond breaks due to the electronic depletion induced in the covalent bond. An application of this study is the modelisation of the forces exerted on the passivated cantilever of an atomic force microscope probing the electron cloud in the contact mode in the Pauli exclusion regime.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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