Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 13, Issue 3, Pages 1044-1056Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.6b00970
Keywords
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Funding
- National Science Foundation [CHE-1361031, CHE-1359769]
- Deutsche Forschungsgemeinschaft (DFG) [GA 370/6-1, 6-2]
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences [DE-AC02-06CH11357]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1361031, 1359769] Funding Source: National Science Foundation
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Benchmark scalar-relativistic coupled-cluster calculations for dissociation energies of the 20 diatomic molecules containing 3d transition metals in the 3dMLBE20 database (J. Chem. Theory Comput. 2015, 11, 2036) are reported. Electron correlation and basis set effects are systematically studied. The agreement between theory and experiment is in general satisfactory. For a subset of 16 molecules, the standard deviation between computational and experimental values is 9 kJ/mol with the maximum deviation being 15 kJ/mol. The discrepancies between theory and experiment remain substantial (more than 20 kJ/mol) for VH, CrH, CoH, and FeH. To explore the source of the latter discrepancies, the analysis used to determine the experimental dissociation energies for VH and CrH is revisited. It is shown that, if improved values are used for the heterolytic C H dissociation energies of di- and trimethylamine involved in the experimental determination, the experimental values for the dissociation energies of VH and CrH are increased by 18 kJ/mol, such that D-0(VH) = 223 +/- 7 kJ/mol and D-0(CrH) = 204 +/- 7 kJ/mol (or D-e(VH) = 233 +/- 7 kJ/mol and D-e(CrH) = 214 +/- 7 kJ/mol). The new experimental values agree quite well with the calculated values, showing the consistency of the computation and the measured reaction thresholds.
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