Coupling Natural Orbital Functional Theory and Many-Body Perturbation Theory by Using Nondynamically Correlated Canonical Orbitals

• Published in: Journal of chemical theory and computation 2021-12, Vol.17 (12), p.7562-7574
• Main Authors: Rodríguez-Mayorga, Mauricio, Mitxelena, Ion, Bruneval, Fabien, Piris, Mario
• Format: Article
• Language: English
• Subjects: Approximation; Correlation; Coupling (molecular); Electron spin; Electronic structure; Mathematical analysis; Orbitals; Perturbation theory; Quantum Electronic Structure
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.1c00858

We develop a new family of electronic structure methods for capturing at the same time the dynamic and nondynamic correlation effects. We combine the natural orbital functional theory (NOFT) and many-body perturbation theory (MBPT) through a canonicalization procedure applied to the natural orbitals to gain access to any MBPT approximation. We study three different scenarios: corrections based on second-order Møller–Plesset (MP2), random-phase approximation (RPA), and coupled-cluster singles doubles (CCSD). Several chemical problems involving different types of electron correlation in singlet and multiplet spin states have been considered. Our numerical tests reveal that RPA-based and CCSD-based corrections provide similar relative errors in molecular dissociation energies (D e) to the results obtained using a MP2 correction. With respect to the MP2 case, the CCSD-based correction improves the prediction, while the RPA-based correction reduces the computational cost.