Molecular Interactions Induced by a Static Electric Field in Quantum Mechanics and Quantum Electrodynamics

• Published in: The journal of physical chemistry letters Vol. 13; no. 9; pp. 2197 - 2204
• Main Authors: Karimpour, Mohammad Reza, Fedorov, Dmitry V, Tkatchenko, Alexandre
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 10.03.2022
• Subjects: Letter; Physical Insights into Materials and Molecular Properties
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.1c04222

By means of quantum mechanics and quantum electrodynamics applied to coupled harmonic Drude oscillators, we study the interaction between two neutral atoms or molecules subject to a uniform static electric field. Our focus is to understand the interplay between leading contributions to field-induced electrostatics/polarization and dispersion interactions, as considered within the employed Drude model for both non-retarded and retarded regimes. For the first case, we present an exact solution for two coupled oscillators obtained by diagonalizing the corresponding quantum-mechanical Hamiltonian and demonstrate that the external field can control the strength of different intermolecular interactions and relative orientations of the molecules. In the retarded regime described by quantum electrodynamics, our analysis shows that field-induced electrostatic and polarization energies remain unchanged (in isotropic and homogeneous vacuum) compared to the non-retarded case. For interacting species modeled by quantum Drude oscillators, the developed framework based on quantum mechanics and quantum electrodynamics yields the leading contributions to molecular interactions under the combined action of external and vacuum fields.