Evaluation of the Bethe Logarithm: From Atom to Chemical Reaction.

J Phys Chem A

ELTE, Eötvös Loránd University, Institute of Chemistry, Pázmány Péter sétány 1/A, BudapestH-1117, Hungary.

Published: January 2023

A general computational scheme for the (nonrelativistic) Bethe logarithm is developed, opening the route to "routine" evaluation of the leading-order quantum electrodynamics correction (QED) relevant for spectroscopic applications for small polyatomic and polyelectronic molecular systems. The implementation relies on the Schwartz method and minimization of a Hylleraas functional. In relation with electronically excited states, a projection technique is considered, which ensures positive definiteness of the functional over the entire parameter (photon momentum) range. Using this implementation, the Bethe logarithm is converged to a relative precision better than 1:10 for selected electronic states of the two-electron H and H, and the three-electron He and H+H molecular systems. The present work focuses on nuclear configurations near the local minimum of the potential energy surface, but the computations can be repeated also for other structures.

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http://dx.doi.org/10.1021/acs.jpca.2c05790DOI Listing

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