The high accuracy extrapolated ab initio thermochemistry (HEAT) protocol is applied to compute the total atomization energy (TAE) and the heat of formation of benzene. Large-scale coupled-cluster calculations with more than 1500 basis functions and 42 correlated electrons as well as zero-point energies based on full cubic and (semi)diagonal quartic force fields obtained with the coupled-cluster singles and doubles with perturbative treatment of the triples method and atomic natural orbital (ANO) triple- and quadruple-zeta basis sets are presented. The performance of modifications to the HEAT scheme and the scaling properties of its contributions with respect to the system size are investigated. A purely quantum-chemical TAE and associated conservative error bar of 5463.0 ± 3.1 kJ mol−1 are obtained, while the corresponding 95% confidence interval, based on a statistical analysis of HEAT results for other and related molecules, is ± 1.8 kJ mol−1. The heat of formation of benzene is determined to be 101.5 ± 2.0 kJ mol−1 and 83.9 ± 2.1 kJ mol−1 at 0 K and 298.15 K, respectively.
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28 July 2011
Research Article|
July 28 2011
Towards highly accurate ab initio thermochemistry of larger systems: Benzene
Michael E. Harding;
Michael E. Harding
a)
1Institut für Physikalische Chemie,
Universität Mainz
, Jakob-Welder-Weg 11, D-55099 Mainz, Germany
2Institute for Theoretical Chemistry, Department of Chemistry and Biochemistry,
The University of Texas at Austin
, Austin, Texas 78712, USA
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Juana Vázquez;
Juana Vázquez
2Institute for Theoretical Chemistry, Department of Chemistry and Biochemistry,
The University of Texas at Austin
, Austin, Texas 78712, USA
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Jürgen Gauss;
Jürgen Gauss
1Institut für Physikalische Chemie,
Universität Mainz
, Jakob-Welder-Weg 11, D-55099 Mainz, Germany
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John F. Stanton;
John F. Stanton
2Institute for Theoretical Chemistry, Department of Chemistry and Biochemistry,
The University of Texas at Austin
, Austin, Texas 78712, USA
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Mihály Kállay
Mihály Kállay
3Department of Physical Chemistry and Materials Science,
Budapest University of Technology and Economics
, Budapest P.O. Box 91, H-1521, Hungary
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a)
Electronic mail: harding@mail.utexas.edu.
J. Chem. Phys. 135, 044513 (2011)
Article history
Received:
March 14 2011
Accepted:
June 20 2011
Citation
Michael E. Harding, Juana Vázquez, Jürgen Gauss, John F. Stanton, Mihály Kállay; Towards highly accurate ab initio thermochemistry of larger systems: Benzene. J. Chem. Phys. 28 July 2011; 135 (4): 044513. https://doi.org/10.1063/1.3609250
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