Coupled cluster theory for positron binding in anions and polyatomic molecules

TL;DR

This paper introduces a coupled cluster method for accurately calculating positron binding energies in molecules, emphasizing the importance of electron correlation and benchmarking against known data.

Contribution

The development of the POS-CCSD method that treats electrons and positrons equally and includes double excitations, advancing the computational modeling of positron-molecule interactions.

Findings

Excellent agreement with quantum Monte Carlo for H−

Highlights the importance of electron correlation in positron binding

Demonstrates the method's applicability to various molecular systems

Abstract

We present the positron coupled cluster singles and doubles (POS-CCSD) method to calculate positron binding energies in molecules. This framework treats electrons and positrons on an equal footing and includes up to simultaneous double-electron-single-positron excitations. We benchmark the approach by computing binding energies for atomic anions and several polar and non-polar polyatomic systems, comparing the results with independent theoretical studies and, where available, experimental data. The fully converged results for H$^{-}$ are in excellent agreement with quantum Monte Carlo and multi-reference configuration interaction results. Quantitative agreement with experiments is not reached in the present study due to the slow convergence of the binding energy with respect to the size of the orbital bases for the electrons and the positron. However, the POS-CCSD results underscore the critical role of electron correlation in the description of electron-positron systems required for a balanced description of these complex systems. In addition, we examine nuclear relaxation effects following positron attachment in LiH.