# Performance of the NOF-MP2 method in hydrogen abstraction reactions

## TL;DR

This paper evaluates the NOF-MP2 method's effectiveness in modeling hydrogen abstraction reactions, demonstrating its accuracy in predicting dissociation energies comparable to CASPT2, especially for systems with multiconfigurational character.

## Contribution

The study provides a comprehensive assessment of NOF-MP2's reliability in describing electron correlation in radical formation and bond cleavage, with validation against experimental and high-level computational data.

## Key findings

- NOF-MP2 achieves quantitative agreement with experimental dissociation energies.
- The method performs comparably to CASPT2 in systems with multiconfigurational character.
- It reliably describes both dynamic and static correlation in radical reactions.

## Abstract

The recently proposed natural orbital functional second-order M{\o}ller-Plesset (NOF-MP2) method is capableof achieving both dynamic and static correlation even for those systems with significant multiconfigurational character. We test its reliability to describe the electron correlation in radical formation reactions, namely, in the homolytic X-H bond cleavage of LiH, BH, CH4, NH3, H2O and HF molecules. Our results are compared with CASSCF and CASPT2 wavefunction calculations and the experimental data. For a dataset of 20 organic molecules, the thermodynamics of C-H homolytic bond cleavage, in which the C-H bond is broken in the presence of different chemical environments, is presented. The radical stabilization energies obtained for such general dataset are compared with the experimental data. It is observed that NOF-MP2 is able to give a quantitative agreement for dissociation energies, with a performance comparable to that of the accurate CASPT2 method.