Journal ArticleDOI
Biorthogonal moment expansions in coupled-cluster theory: Review of key concepts and merging the renormalized and active-space coupled-cluster methods
Jun Shen,Piotr Piecuch +1 more
- Vol. 401, pp 180-202
TLDR
In this article, the authors proposed a flexible MMCC (Flex-MMCC) formalism to correct the results of the CC calculations with singles, doubles, and active-space triples for the remaining effects due to connected triple excitations that are missing in the CCSDt considerations.Abstract:
After reviewing recent progress in the area of the development of coupled-cluster (CC) methods for quasi-degenerate electronic states that are characterized by stronger non-dynamical correlation effects, including new generations of single- and multi-reference approaches that can handle bond breaking and excited states dominated by many-electron transitions, and after discussing the key elements of the left-eigenstate completely renormalized (CR) CC and equation-of-motion (EOM) CC methods, and the underlying biorthogonal method of moments of CC (MMCC) equations [P. Piecuch, M. Wloch, J. Chem. Phys. 123 (2005) 224105; P. Piecuch, M. Wloch, J.R. Gour, A. Kinal, Chem. Phys. Lett. 418 (2006) 467; M. Wloch, M.D. Lodriguito, P. Piecuch, J.R. Gour, Mol. Phys. 104 (2006) 2149], it is argued that it is beneficial to merge the CR-CC/EOMCC and active-space CC/EOMCC [P. Piecuch, Mol. Phys. 108 (2010) 2987, and references therein] theories into a single formalism. In order to accomplish this goal, the biorthogonal MMCC theory, which provides compact many-body expansions for the differences between the full configuration interaction and CC or, in the case of excited states, EOMCC energies, obtained using conventional truncation schemes in the cluster operator T and excitation operator Rμ, is generalized, so that one can correct the CC/EOMCC energies obtained with arbitrary truncations in T and Rμ for the selected many-electron correlation effects of interest. The resulting moment expansions, defining the new, Flexible MMCC (Flex-MMCC) formalism, and the ensuing CC(P; Q) hierarchy, proposed in the present work, enable one to correct energies obtained in the active-space CC and EOMCC calculations, in which one selects higher many-body components of T and Rμ via active orbitals and which recover much of the relevant non-dynamical and some dynamical electron correlation effects in applications involving potential energy surfaces (PESs) along bond breaking coordinates, for the effects of higher-order, primarily dynamical, correlations missing in the active-space CC/EOMCC considerations. The Flex-MMCC corrections to the active-space CC/EOMCC energies are mathematically similar to the non-iterative energy corrections defining the existing left-eigenstate CR-CC and CR-EOMCC methods, such as CR-CC(2, 3) and CR-EOMCC(2, 3). The potential advantages of the Flex-MMCC and CC(P; Q) formalisms are illustrated by describing the initial implementation and numerical tests of the novel CC hybrid scheme, abbreviated as CC(t; 3), in which one corrects the results of the CC calculations with singles, doubles, and active-space triples, termed CCSDt, for the remaining effects due to connected triple excitations that are missing in the CCSDt considerations, but are present in the MMCC-based CR-CC(2, 3) approach. By examining bond breaking in the HF, F2, and F 2 + molecules, it is demonstrated that the CC(t; 3) method improves the CCSDt and CR-CC(2, 3) results, providing PESs that agree with those obtained with the full CC theory with singles, doubles, and triples (CCSDT) to within small fractions of a millihartree, at the fraction of the computer costs of the CCSDT calculations. Different strategies for defining active-space triples within the CC(t; 3) scheme and the underlying CCSDt method are discussed. When limited to the ground-state problem, the CC(t; 3) approach can be regarded as an improved and rigorously derived extension of the recently proposed CCSD(T)-h method [J. Shen, E. Xu, Z. Kou, S. Li, J. Chem. Phys. 132 (2010) 114115], in which triples corrections of the CCSD(T) type are replaced by their more robust CR-CC(2, 3)-style analogs.read more
Citations
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Journal ArticleDOI
Recent developments in the general atomic and molecular electronic structure system.
Giuseppe M. J. Barca,Colleen Bertoni,Laura Carrington,Dipayan Datta,Nuwan De Silva,J. Emiliano Deustua,Dmitri G. Fedorov,Jeffrey R. Gour,Anastasia O. Gunina,Emilie B. Guidez,Taylor Harville,Stephan Irle,Joe Ivanic,Karol Kowalski,Sarom S. Leang,Hui Li,Wei Li,Jesse J. Lutz,Ilias Magoulas,Joani Mato,Vladimir Mironov,Hiroya Nakata,Buu Q. Pham,Piotr Piecuch,David Poole,Spencer R. Pruitt,Alistair P. Rendell,Luke Roskop,Klaus Ruedenberg,Tosaporn Sattasathuchana,Michael W. Schmidt,Jun Shen,Lyudmila V. Slipchenko,Masha Sosonkina,Vaibhav Sundriyal,Ananta Tiwari,Jorge L. Galvez Vallejo,Bryce Westheimer,Marta Włoch,Peng Xu,Federico Zahariev,Mark S. Gordon +41 more
TL;DR: A discussion of many of the recently implemented features of GAMESS (General Atomic and Molecular Electronic Structure System) and LibCChem (the C++ CPU/GPU library associated with GAMESS) is presented, which include fragmentation methods, hybrid MPI/OpenMP approaches to Hartree-Fock, and resolution of the identity second order perturbation theory.
Journal ArticleDOI
Psi4 1.4: Open-source software for high-throughput quantum chemistry
Daniel G. A. Smith,Lori A. Burns,Andrew C. Simmonett,Robert M. Parrish,Matthew C. Schieber,Raimondas Galvelis,Peter Kraus,Holger Kruse,Roberto Di Remigio,Asem Alenaizan,Andrew M. James,Susi Lehtola,Jonathon P. Misiewicz,Maximilian Scheurer,Robert A. Shaw,Jeffrey B. Schriber,Yi Xie,Zachary L. Glick,Dominic A. Sirianni,Joseph Senan O’Brien,Jonathan M. Waldrop,Ashutosh Kumar,Edward G. Hohenstein,Benjamin P. Pritchard,Bernard R. Brooks,Henry F. Schaefer,Alexander Yu. Sokolov,Konrad Patkowski,A. Eugene DePrince,Uğur Bozkaya,Rollin A. King,Francesco A. Evangelista,Justin M. Turney,T. Daniel Crawford,C. David Sherrill +34 more
TL;DR: A rewrite of the top-level computation driver, and concomitant adoption of the MolSSI QCARCHIVE INFRASTRUCTURE project, makes the latest version of PSI4 well suited to distributed computation of large numbers of independent tasks.
Journal ArticleDOI
Discrepancy between experimental and theoretical β-decay rates resolved from first principles
P. Gysbers,P. Gysbers,Gaute Hagen,Gaute Hagen,Jason D. Holt,Gustav R. Jansen,Gustav R. Jansen,T. D. Morris,T. D. Morris,Petr Navrátil,Thomas Papenbrock,Thomas Papenbrock,Sofia Quaglioni,Achim Schwenk,Achim Schwenk,S. R. Stroberg,S. R. Stroberg,S. R. Stroberg,Kyle Wendt +18 more
TL;DR: In this paper, the authors show that the difference between the β-decay rate predicted for free neutrons and that measured in real nuclei is explained by strong correlations and the weak-force coupling between nucleons.
Journal ArticleDOI
Discrepancy between experimental and theoretical $\beta$-decay rates resolved from first principles.
P. Gysbers,Gaute Hagen,Jason D. Holt,Gustav R. Jansen,T. D. Morris,Petr Navrátil,Thomas Papenbrock,Sofia Quaglioni,Achim Schwenk,S. R. Stroberg,Kyle Wendt +10 more
TL;DR: In this article, it was shown that the observed β-decay rates of free neutrinos are systematically smaller than theoretical predictions, and that this quenching arises to a large extent from the coupling of the weak force to two nucleons as well as from strong correlations in the nucleus.
Journal ArticleDOI
Spin-State Energetics of Heme-Related Models from DFT and Coupled Cluster Calculations.
TL;DR: An efficient computational protocol is proposed-based on the mix of extrapolation to complete basis set and explicitly correlated (F12) methodology-which retains the high accuracy of the CCSD(T) method at a cost that makes it applicable also to relatively large models, e.g., FeP and FeP(Cl) (P = porphin).
References
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A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples
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Journal ArticleDOI
On the Correlation Problem in Atomic and Molecular Systems. Calculation of Wavefunction Components in Ursell-Type Expansion Using Quantum-Field Theoretical Methods
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