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Molecular Physics
An International Journal at the Interface Between Chemistry and Physics
Volume 110, 2012 - Issue 19-20: Special Issue in Honour of Peter R. Taylor
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Invited Articles

Further benchmarks of a composite, convergent, statistically calibrated coupled-cluster-based approach for thermochemical and spectroscopic studies

David Feller Department of Chemistry, Washington State University, Pullman, Washington 99164-4630, USACorrespondence[email protected]
,
Kirk A. Peterson Department of Chemistry, Washington State University, Pullman, Washington 99164-4630, USA
&
David A. Dixon Chemistry Department, The University of Alabama, Shelby Hall, Tuscaloosa, Alabama 35487-0336, USA
Pages 2381-2399 | Received 28 Feb 2012, Accepted 05 Apr 2012, Published online: 25 May 2012
 
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Abstract

A flexible, high-level, composite approach based on coupled cluster theory has been used to predict the atomization energies and equilibrium structures of 13 small, first-row compounds. Each of the major components in this approach can be systematically improved, thereby providing a practical measure of the inherent uncertainty (or degree of convergence) in the final results. Comparison with Active Thermochemical Table data, which relies on a network of experimental and theoretical data, showed excellent agreement for the atomization energies. With the addition of the latest molecular systems to the Computational Results Database, the composite approach was found to yield a mean absolute deviation of 0.19 kcal mol−1 and a root-mean-square deviation of 0.31 kcal mol−1 across 142 comparisons. If the analysis is limited to experimental data with estimated uncertainties of 0.2 kcal mol−1 or less, the error metrics are cut in half. Similar good agreement is found with experimental structures, but the relative scarcity of accurate equilibrium structures limits the significance of the statistical analysis. Unavoidably, many of the comparisons could not be made with r e structural parameters. Explicitly correlated methods were found to be effective at replicating results obtained from the standard method with large basis sets, thereby reducing the high computational cost for several of the components.

Acknowledgements

Dr. Branko Ruscic is thanked for his comments about the ATcT data on N2O4. This work was supported by the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, U.S. Department of Energy (DOE) under grant No. DE-FG02-03ER15481 (catalysis center program). DAD also thanks the Robert Ramsay Chair Fund of The University of Alabama and Argonne National Laboratory for support.

Supporting information available

Supporting information containing the raw CCSD(T)(FC) results with the largest basis sets is available.

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