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Title: Prediction of Bond Dissociation Energies/Heats of Formation for Diatomic Transition Metal Compounds: CCSD(T) Works

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [1];  [2]; ORCiD logo [1]
  1. Univ. of Alabama, Tuscaloosa, AL (United States)
  2. Washington State Univ., Pullman, WA (United States)
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It was recently reported that the coupled cluster singles and doubles with perturbative triples method, CCSD(T), should not be used as a benchmark tool for the prediction of dissociation energies (heats of formation) for the 1st row transition metal diatomics based on a comparison with the experimental thermodynamic values for a set of 20 diatomics. In the present work reported here, the bond dissociation energies as well as the heats of formation for those diatomics have been calculated by the Feller-Peterson-Dixon approach at the CCSD(T)/complete basis set (CBS) level of theory including scalar relativistic corrections and correlation of the outer shell of core electrons in addition to the valence electrons. Revised experimental values for the hydrides are presented that are based on new heterolytic R-H bond dissociation energies, which are needed for analysis of the mass spectrometry experiments. The agreement between the calculated bond dissociation energies and the revised experimental values of the hydrides is good. Good agreement of the calculated bond dissociation energies/heats of formation is also found for most of the chlorides, oxides, and sulfides given the experimental error bars from experiment and those of the transition metal atoms in the gas phase. Thus, reliable results can be achieved by the CCSD(T) method at the CBS limit. The use of PW91 orbitals for the CCSD(T) calculations improves the predictions for some compounds with large T1 diagnostics at the HF-CCSD(T) level. The optimized bond distances and calculated vibrational frequencies for the diatomics also agree well with the available experimental values.

Research Organization:
Washington State Univ., Pullman, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
FG02-03ER15481; SC0008501; FG02-12ER16329
OSTI ID:
1534558
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: 74 works
Citation information provided by
Web of Science

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Cited By (11)

Estimating the intrinsic limit of the Feller-Peterson-Dixon composite approach when applied to adiabatic ionization potentials in atoms and small molecules journal July 2017
Comparative study of electronic-structure methods for platinum-containing molecules: bond lengths and bond dissociation energies journal July 2019
Bond energy of ThN + : A guided ion beam and quantum chemical investigation of the reactions of thorium cation with N 2 and NO journal July 2019
Performance of Density Functional Theory for Transition Metal Oxygen Bonds journal October 2019
Gas Phase Hydrolysis and Oxo‐Exchange of Actinide Dioxide Cations: Elucidating Intrinsic Chemistry from Protactinium to Einsteinium journal January 2019
Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals journal April 2017
New insights into Fe–H$$_{2}$$ and Fe–H$$^{-}$$ bonding of a [NiFe] hydrogenase mimic: a local vibrational mode study journal May 2019
High-level ab initio predictions for the ionisation energy, bond dissociation energies and heats of formation of zirconium oxide and its cation (ZrO/ZrO + ) journal March 2018
Metal–Halogen Bonding Seen through the Eyes of Vibrational Spectroscopy journal December 2019
Performance of density functionals for the structure and energetics of (M–O) 0,± (M=Al, Si, Sc–Zn) journal December 2018
Polishing the Gold Standard: The Role of Orbital Choice in CCSD(T) Vibrational Frequency Prediction text January 2020

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry
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Bond cleavage
Oxides
Anions
Transition metals