Toward a muon-specific electronic structure theory: Effective electronic Hartree-Fock equations for the muonic molecules

TL;DR

This paper develops an effective Hartree-Fock method tailored for muonic molecules, simplifying the treatment of muons as quantum oscillators into an effective potential for electrons, enabling efficient computational studies.

Contribution

It introduces a novel effective HF framework for muonic systems, incorporating muon-electron interactions into an optimized potential, distinct from traditional two-component approaches.

Findings

Successfully implemented for second and third row muonic molecules.

Designed muon-specific Gaussian basis sets with distinct exponents.

Demonstrated the method's potential for broader muonic system applications.

Abstract

An effective set of the Hartree-Fock (HF) equations are derived for electrons of the muonic systems, i.e., molecules containing a positively charged muon, conceiving the muon as a quantum oscillator, which are completely equivalent to the usual two-component HF equations used to derive stationary states of the muonic molecules. In these effective equations, a non-Coulombic potential is added to the orthodox coulomb and exchange potential energy terms, which describes the interaction of the muon and the electrons effectively and is optimized during the self-consistent field cycles. While in the two-component HF equations muon is treated as a quantum wave, in the effective HF equations it is absorbed into the effective potential and practically transformed into an effective potential field experienced by electrons. The explicit form of the effective potential depends on the nature of muon vibrations and is derivable from the basis set used to expand the muonic spatial orbital. The resulting effective Hartree-Fock equations are implemented computationally and used successfully, as a proof of concept, in a series of the muonic molecules containing all atoms from the second and third rows of the Periodic Table. To solve the algebraic version of the equations muon-specific gaussian basis sets are designed for both muon and surrounding electrons and it is demonstrated that the optimized exponents are quite distinct from those derived for the hydrogen isotopes. The developed effective HF theory is quite general and in principle can be used for any muonic system while it is the starting point for a general effective electronic structure theory that incorporates various types of quantum correlations into the muonic systems beyond the HF equations.