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Title: Bond Dissociation Energies for Diatomic Molecules Containing 3d Transition Metals: Benchmark Scalar-Relativistic Coupled-Cluster Calculations for 20 Molecules

Journal Article · · Journal of Chemical Theory and Computation
ORCiD logo [1];  [2];  [3]; ORCiD logo [4]; ORCiD logo [5]
  1. Univ. of Texas, Austin, TX (United States). Dept. of Chemistry. Inst. for Theoretical Chemistry; Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Chemistry
  2. Univ. of Mainz (Germany). Inst. of Physical Chemistry
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division; Univ. of Chicago, IL (United States). Computation Inst.
  4. Univ. of Utah, Salt Lake City, UT (United States). Dept. of Chemistry
  5. Univ. of Texas, Austin, TX (United States). Dept. of Chemistry. Inst. for Theoretical Chemistry
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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 in this paper. 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 D0(VH) = 223 ± 7 kJ/mol and D0(CrH) = 204 ± 7 kJ/mol (or De(VH) = 233 ± 7 kJ/mol and De(CrH) = 214 ± 7 kJ/mol). Finally, the new experimental values agree quite well with the calculated values, showing the consistency of the computation and the measured reaction thresholds.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Texas, Austin, TX (United States); Univ. of Utah, Salt Lake City, UT (United States); Univ. of Mainz (Germany)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); German Research Foundation (DFG)
Contributing Organization:
Univ. of Chicago, IL (United States); Johns Hopkins Univ., Baltimore, MD (United States)
Grant/Contract Number:
AC02-06CH11357; CHE-1361031; CHE-1359769; GA 370/6-1; GA 370/6-2
OSTI ID:
1368564
Journal Information:
Journal of Chemical Theory and Computation, Vol. 13, Issue 3; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 66 works
Citation information provided by
Web of Science

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Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals journal April 2017
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Active Thermochemical Tables
Bond dissociation energy
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