Na minha lista:
| Main Authors: | , , , |
|---|---|
| Formato: | Preprint |
| Publicado em: |
2026
|
| Assuntos: | |
| Acesso em linha: | https://arxiv.org/abs/2602.04420 |
| Tags: |
Adicionar Tag
Sem tags, seja o primeiro a adicionar uma tag!
|
Sumário:
- 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 $π\to π^*$, $n \to π^*$, 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.