Many-body theory predictions of positron binding energies in five-membered heterocycles involving N, O, S and NH substituents

TL;DR

This study uses advanced many-body theory calculations to predict positron binding energies and analyze positron localization in five-membered heterocycles with various substituents, revealing the influence of molecular structure.

Contribution

It introduces all-order many-body calculations of positron binding energies in heterocycles using the { t EXCITON+} code, incorporating complex correlation effects and analyzing substituent impacts.

Findings

Positron tends to localize near N, S, O, then NH substituents.

Substituent substitution significantly affects positron binding energies.

Molecular orbitals contribute variably to the correlation potential.

Abstract

Positron binding energies and Dyson orbitals for five-membered heterocycles with N, O, S and NH substituents are predicted \emph{ab initio} via many-body theory. The positron-molecule correlation potential (self energy) is calculated via solution of Bethe-Salpeter equations that describe the positron-induced polarization of the target and screening of the electron-positron Coulomb interaction at the $GW$@BSE level, the infinite electron-positron ladder series that describes the crucially important process of virtual positronium formation, and the analogous positron-hole ladder series. The all-order calculations employ Gaussian-orbital bases and are implemented in the {\tt EXCITON+} code. The effect of substituting combinations of N, O and S atoms, and the NH group in the molecule's ring is studied, and the role of individual molecular orbitals, many of which are found to significantly contribute to the correlation potential, quantified. Analysis of the positron bound-state Dyson orbitals shows that the positron is typically localized next to one or two of the substituents in the ring, with the order of preference N, S, O, then NH, and is also influenced by aromaticity and the presence of double ($\pi$) bonds in the ring.