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      Accurate Reduced-Cost CCSD(T) Energies: Parallel Implementation, Benchmarks, and Large-Scale Applications

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          Abstract

          The accurate and systematically improvable frozen natural orbital (FNO) and natural auxiliary function (NAF) cost-reducing approaches are combined with our recent coupled-cluster singles, doubles, and perturbative triples [CCSD(T)] implementations. Both of the closed- and open-shell FNO-CCSD(T) codes benefit from OpenMP parallelism, completely or partially integral-direct density-fitting algorithms, checkpointing, and hand-optimized, memory- and operation count effective implementations exploiting all permutational symmetries. The closed-shell CCSD(T) code requires negligible disk I/O and network bandwidth, is MPI/OpenMP parallel, and exhibits outstanding peak performance utilization of 50–70% up to hundreds of cores. Conservative FNO and NAF truncation thresholds benchmarked for challenging reaction, atomization, and ionization energies of both closed- and open-shell species are shown to maintain 1 kJ/mol accuracy against canonical CCSD(T) for systems of 31–43 atoms even with large basis sets. The cost reduction of up to an order of magnitude achieved extends the reach of FNO-CCSD(T) to systems of 50–75 atoms (up to 2124 atomic orbitals) with triple- and quadruple-ζ basis sets, which is unprecedented without local approximations. Consequently, a considerably larger portion of the chemical compound space can now be covered by the practically “gold standard” quality FNO-CCSD(T) method using affordable resources and about a week of wall time. Large-scale applications are presented for organocatalytic and transition-metal reactions as well as noncovalent interactions. Possible applications for benchmarking local CCSD(T) methods, as well as for the accuracy assessment or parametrization of less complete models, for example, density functional approximations or machine learning potentials, are also outlined.

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          Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy.

          Gaussian basis sets of quadruple zeta valence quality for Rb-Rn are presented, as well as bases of split valence and triple zeta valence quality for H-Rn. The latter were obtained by (partly) modifying bases developed previously. A large set of more than 300 molecules representing (nearly) all elements-except lanthanides-in their common oxidation states was used to assess the quality of the bases all across the periodic table. Quantities investigated were atomization energies, dipole moments and structure parameters for Hartree-Fock, density functional theory and correlated methods, for which we had chosen Møller-Plesset perturbation theory as an example. Finally recommendations are given which type of basis set is used best for a certain level of theory and a desired quality of results.
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            Quantum Theory of Many-Particle Systems. I. Physical Interpretations by Means of Density Matrices, Natural Spin-Orbitals, and Convergence Problems in the Method of Configurational Interaction

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              Energy-adjustedab initio pseudopotentials for the second and third row transition elements

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                Author and article information

                Journal
                J Chem Theory Comput
                J Chem Theory Comput
                ct
                jctcce
                Journal of Chemical Theory and Computation
                American Chemical Society
                1549-9618
                1549-9626
                05 January 2021
                09 February 2021
                : 17
                : 2
                : 860-878
                Affiliations
                Department of Physical Chemistry and Materials Science, Budapest University of Technology and Economics , P.O. Box 91, H-1521 Budapest, Hungary
                Author notes
                Article
                10.1021/acs.jctc.0c01077
                7884001
                33400527
                fa688f98-264a-44d0-88a7-1421e567de59
                © 2021 The Authors. Published by American Chemical Society

                This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.

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                ct0c01077
                ct0c01077

                Computational chemistry & Modeling
                Computational chemistry & Modeling

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