A configuration interaction correction on top of pair coupled cluster doubles

Abstract

Numerous numerical studies have shown that geminal-based methods are a promising direction to model strongly correlated systems with low computational costs. Several strategies have been introduced to capture the missing dynamical correlation effects, which typically exploit \textit{a posteriori} corrections to account for correlation effects associated with broken-pair states or inter-geminal correlations. In this article, we scrutinize the accuracy of the pair coupled cluster doubles (pCCD) method extended by configuration interaction (CI) theory. Specifically, we benchmark various CI models, including, at most double excitations against selected CC corrections as well as conventional single-reference CC methods. A simple Davidson correction is also tested. The accuracy of the proposed pCCD-CI approaches is assessed for challenging small model systems such as the \ce{N2} and \ce{F2} dimers and various di- and triatomic actinide-containing compounds. In general, the proposed CI methods considerably improve spectroscopic constants compared to the conventional CCSD approach, provided a Davidson correction is included in the theoretical model. At the same time, their accuracy lies between the linearized frozen pCCD and frozen pCCD variants.

arXiv comment4 figures

References in corpus (29)

• Order of Magnitude Smaller Limit on the Electric Dipole Moment of the Electron
• Ab Initio Quantum Chemistry using the Density Matrix Renormalization Group
• The Density Matrix Renormalization Group in Chemistry and Molecular Physics: Recent Developments and New Challenges
• Tensor product methods and entanglement optimization for ab initio quantum chemistry
• Multireference Correlation in Long Molecules with the Quadratic Scaling Density Matrix Renormalization Group
• Entanglement Measures for Single- and Multi-Reference Correlation Effects
• Seniority-based coupled cluster theory
• Efficient description of strongly correlated electrons with mean-field cost
• Orbital entanglement in quantum chemistry
• Prospects for an electron electric dipole moment search in metastable ThO and ThF${}^{+}$
• Combined 4-component and relativistic pseudopotential study of ThO for the electron electric dipole moment search
• Projected seniority-two orbital optimization of the Antisymmetric Product of one-reference orbital Geminal
• Linearized Coupled Cluster Correction on the Antisymmetric Product of 1 reference orbital Geminals
• Second-Order Self-Consistent-Field Density-Matrix Renormalization Group
• Theoretical study of thorium monoxide for the electron electric dipole moment search, II: Electronic properties of $H^3{\Delta }_1$ in ThO
• Excited States From State Specific Orbital Optimized Pair Coupled Cluster
• Electron Electric Dipole Moment and Hyperfine Interaction Constants for ThO
• T3NS: three-legged tree tensor network states
• Analysis of two-orbital correlations in wavefunctions restricted to electron-pair states
• Targeting doubly-excited states with Equation of Motion Coupled Cluster theory restricted to double excitations
• Geminal-Based Configuration Interaction
• Pythonic Black-box Electronic Structure Tool (PyBEST). An open-source Python platform for electronic structure calculations at the interface between chemistry and physics
• Benchmarking the accuracy of seniority-zero wavefunction methods for non-covalent interactions
• Orbital entanglement and correlation from pCCD-tailored Coupled Cluster wave functions
• On the Multi-Reference Nature of Plutonium Oxides: PuO${}_2^{2+}$, PuO${}_2$, PuO${}_3$ and PuO${}_2$(OH)${}_2$
• Modeling the electronic structures of the ground and excited states of the ytterbium atom and the ytterbium dimer: A modern quantum chemistry perspective
• Assessing the accuracy of simplified Coupled Cluster methods for electronic excited states in f0 actinide compounds
• Actinide chemistry using singlet-paired coupled cluster and its combinations with density functionals
• Electron correlation effects of the ThO and ThS molecules in the spinor basis. A relativistic coupled cluster study of ground and excited states properties

Cited by in corpus (10)

• The relationship between structure and excited-state properties in polyanilines from geminal-based methods
• Seniority and Hierarchy Configuration Interaction for Radicals and Excited States
• Linear Response pCCD-Based Methods: LR-pCCD and LR-pCCD+S Approaches for the Efficient and Reliable Modeling of Excited state Properties
• Delving into the Catalytic Mechanism of Molybdenum Cofactors: A Novel Coupled Cluster Study
• Benchmarking ionization potentials from the simple pCCD model
• Simple and efficient computational strategies for calculating orbital energies and pair-orbital energies from pCCD-based methods
• DMRG-tailored coupled cluster method in the 4c-relativistic domain: General implementation and application to the NUHFI and NUF${}_3$ molecules
• Seniority-zero Linear Canonical Transformation Theory
• Jordan-Wigner Transformation for the Description of Strong Correlation in Fermionic Systems
• Partial separability of the Schroedinger equation combined with a Jastrow factor