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“Best” Iterative Coupled-Cluster Triples Model? More Evidence for 3CC

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
To follow up on the unexpectedly good performance of several coupled-cluster models with approximate inclusion of 3-body clusters we performed a more complete assessment of the 3CC method for accurate computational thermochemistry in the standard HEAT framework. New spin-integrated implementation of the 3CC method applicable to closed- and open-shell systems utilizes a new automated toolchain for derivation, optimization, and evaluation of operator algebra in many-body electronic structure. We found that with a double-ζ basis set the 3CC correlation energies and their atomization energy contributions are almost always more accurate (with respect to the CCSDTQ reference) than the CCSDT model as well as the standard CCSD(T) model. The mean absolute errors in cc-pVDZ {3CC, CCSDT, and CCSD(T)} electronic (per valence electron) and atomization energies relative to the CCSDTQ reference for the HEAT data set, were {24, 70, 122} μEh/e and {0.46, 2.00, 2.58} kJ/mol, respectively. The mean absolute errors in the complete-basis-set limit {3CC, CCSDT, and CCSD(T)} atomization energies relative to the HEAT model reference, were {0.52, 2.00, and 1.07} kJ/mol, The significant and systematic reduction of the error by the 3CC method and its lower cost than CCSDT suggests it as a viable candidate for post- CCSD(T) thermochemistry applications, as well as the preferred alternative to CCSDT in general.
Research Organization:
Virginia Polytechnic Institute and State University (Virginia Tech), Blacksburg, VA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0022263
OSTI ID:
2475666
Alternate ID(s):
OSTI ID: 2477577
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 45 Vol. 128; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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