UGA-SSMRPT2 -- A Multireference Perturbation Theory Predicting Accurate Electronic Excitation Energies in Diverse Molecular Systems

TL;DR

UGA-SSMRPT2 is a new multireference perturbation theory that accurately predicts electronic excitation energies across diverse molecular systems, offering a size-extensive, intruder-free, and computationally efficient alternative to existing methods.

Contribution

This work introduces UGA-SSMRPT2, a novel spin-free perturbative approach that achieves high accuracy for excitation energies with fewer active spaces and avoids intruder states without empirical parameters.

Findings

Achieves near-chemical accuracy within 0.20 eV of EOM-CCSD.

Surpasses popular MRPT2 methods like NEVPT2, CASPT2, and MCQDPT.

Requires smaller active spaces and avoids intruder states.

Abstract

UGA-SSMRPT2, the spin-free perturbative analogue of Mukerjee's State-Specific Multireference Coupled Cluster Theory (MkMRCC) is known to be successful for size-extensive and intruder-free construction of dissociation curves. This work demonstrates that UGA-SSMRPT2 is also an accurate and computationally inexpensive framework for computing excitation energies. The method achieves near-chemical accuracy for the vast majority of $\pi \to \pi^*$, $n \to \pi^*$, charge-transfer, valence-Rydberg and Rydberg excited states commonly used for benchmarking electronic structure theories for excited states. Our results demonstrate that UGA-SSMRPT2 excitation energies lie within 0.20 eV of EOM-CCSD and/or well-established theoretical best estimates often surpassing the popular MRPT2 approaches like NEVPT2, CASPT2, and MCQDPT while typically requiring smaller active spaces. Its state-specific formulation circumvents the well-known intruder-state problem and eliminates the need for empirical parameters such as IPEA shifts in CASPT2. This work proposes UGA-SSMRPT2 as a robust, and scalable approach for modeling challenging electronic excited states.