Unitary Coupled-Cluster based Self-Consistent Electron Propagator Theory for Electron-Detached and Electron-Attached States: A Quadratic Unitary Coupled-Cluster Singles and Doubles Method and Benchmark Calculations

TL;DR

This paper introduces a new unitary coupled-cluster based self-consistent electron propagator theory for accurately describing electron attachment and detachment states, demonstrating superior performance over existing methods in benchmark tests.

Contribution

It develops and implements the IP/EA-UCC3 and IP/EA-qUCCSD schemes within the UCCSD framework, achieving high accuracy in ionization potential calculations without triple excitations.

Findings

IP-qUCCSD achieves MAD of 0.19 eV, outperforming some higher-order methods.

The methods show comparable accuracy for electron affinity calculations.

Benchmark results validate the effectiveness of the proposed UCC-based EPT approaches.

Abstract

A unitary coupled-cluster (UCC)-based self-consistent electron propagator theory (EPT) is proposed for the description of electron-detached and electron-attached states. Two practical schemes, termed IP/EA-UCC3 and IP/EA-qUCCSD, are developed and implemented within the UCC singles and doubles (UCCSD) framework using the perturbative and commutator-based truncation strategies for the similarity-transformed Hamiltonian $\bar{H}$. The numerical performance of these UCC-based EPT methods is evaluated primarily using full configuration interaction (FCI) reference data and compared with established approaches, including IP/EA-ADC(3), IP/EA-ADC(4) and IP/EA-EOM-CCSD. Benchmark calculations demonstrate that IP-qUCCSD achieves the highest overall accuracy among Hermitian ionized-state methods for one-hole (1h)-dominated IPs of closed-shell systems, with a mean absolute deviation (MAD) of 0.19 eV and standard deviation (SD) of 0.13 eV. Remarkably, despite the absence of triple-excitation contributions, IP-qUCCSD outperforms the higher-order ADC(4) method. For one-particle (1p)-dominated EA calculations, all tested methods exhibit comparable accuracy.