Can second-order perturbation theory accurately predict electron density of open-shell molecules? The importance of self-consistency

TL;DR

This study evaluates the OBMP2 method for predicting electron densities in open-shell molecules, demonstrating its accuracy and efficiency compared to standard methods and its potential as a practical alternative to higher-level theories.

Contribution

The paper introduces and assesses the OBMP2 method, showing it outperforms standard MP2 and DFT, and rivals CCSD in accuracy for open-shell systems.

Findings

OBMP2 outperforms MP2 and DFT in all tested cases.

OBMP2's accuracy is comparable to CCSD.

OBMP2 is effective for predicting electron densities in open-shell molecules.

Abstract

Electron density distribution plays an essential role in predicting molecular properties. It is also a simple observable from which machine-learning models for molecular electronic structure can be derived. In the present work, we present the performance of the one-body M{\o}ller-Plesset second-order perturbation (OBMP2) theory that we have recently developed. In OBMP2, an effective one-body Hamiltonian including dynamic correlation at the MP2 level is derived using the canonical transformation followed by the cumulant approximation. We evaluate electron density and related properties of three groups of open-shell systems: atoms and their ions, main-group radicals, and halogen dimmers. We find that OBMP2 outperforms standard MP2 and density functional theory in all cases considered here, and its accuracy is comparable to coupled-cluster singles and doubles (CCSD), a higher-level method. OBMP2 is thus believed to be an effective method for predicting the accurate electron density of open-shell molecules.