# Benchmark of dynamic electron correlation models for seniority-zero wavefunctions and their application to thermochemistry

## TL;DR

This paper develops and benchmarks new perturbation theory models combined with AP1roG wavefunctions to accurately describe both static and dynamic electron correlation effects, improving thermochemistry predictions.

## Contribution

The authors extend perturbation theory models with AP1roG to include dynamic correlation, and benchmark their performance against high-level reference data for reaction energies and bond-breaking processes.

## Key findings

- Linearized coupled cluster correction performs best among tested models.
- Second-order perturbation theory with specific Hamiltonian choices yields reliable results.
- Models accurately describe systems with both static and dynamic electron correlation.

## Abstract

Wavefunctions restricted to electron-pair states are promising models to describe static/nondynamic electron correlation effects encountered, for instance, in bond-dissociation processes and transition-metal and actinide chemistry. To reach spectroscopic accuracy, however, the missing dynamic electron correlation effects that cannot be described by electron-pair states need to be included \textit{a posteriori}. In this article, we extend the previously presented perturbation theory models with an Antisymmetric Product of 1-reference orbital Geminal (AP1roG) reference function that allow us to describe both static/nondynamic and dynamic electron correlation effects. Specifically, our perturbation theory models combine a diagonal and off-diagonal zero-order Hamiltonian, a single-reference and multi-reference dual state, and different excitation operators used to construct the projection manifold. We benchmark all proposed models as well as an \textit{a posteriori} linearized coupled cluster correction on top of AP1roG against CR-CCSD(T) reference data for reaction energies of several closed-shell molecules that are extrapolated to the basis set limit. Moreover, we test the performance of our new methods for multiple bond breaking processes in the N$_2$, C$_2$, and BN dimers against MRCI-SD and MRCI-SD+Q reference data. Our numerical results indicate that the best performance is obtained from a linearized coupled cluster correction as well as second-order perturbation theory corrections employing a diagonal and off-diagonal zero-order Hamiltonian and a single-determinant dual state. These dynamic corrections on top of AP1roG allow us to reliably model molecular systems dominated by static/nondynamic as well as dynamic electron correlation.