Year: 2025
Type: article
Abstract: We present an implementation of Coupled Cluster Singles, Doubles, and Perturbative Triples [CCSD(T)] density matrix evaluation, integrated within the Bootstrap Embedding (BE2) framework, and accelerated through the use of orbital permutation symmetry. Our approach achieves a substantial reduction in computational cost compared to canonical all-electron CCSD(T) calculations while retaining high accuracy in relative energies. Benchmark calculations on annulene systems show that BE2-CCSD(T) achieves accurate energetics with near-linear scaling in system size, enabling routine application to systems that are otherwise intractable with conventional post-Hartree-Fock methods using both double- and triple-ζ basis sets. We then benchmark the BE2-CCSD(T) scheme with Intrinsic Atomic Orbital and Projected Atomic Orbital (IAO + PAO) partitioning versus canonical CCSD(T) in isomerizations. This work lays the groundwork for extending fragment-based correlated wave function methods to broader classes of molecular systems.
Author: Yi Sun
Institution: University of Chicago
Language: English
Subfield: Atomic and Molecular Physics, and Optics
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W4415629216