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  Correlated Ab Initio and Density Functional Studies on H2 Activation by FeO+

Altun, A., Breidung, J., Neese, F., & Thiel, W. (2014). Correlated Ab Initio and Density Functional Studies on H2 Activation by FeO+. Journal of Chemical Theory and Computation, 10(9), 3807-3820. doi:10.1021/ct500522d.

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 Creators:
Altun, Ahmet1, Author
Breidung, Jürgen2, Author              
Neese, Frank3, Author              
Thiel, Walter2, Author              
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1Department of Physics, Fatih University, 34500 B.Çekmece, Istanbul, Turkey, ou_persistent22              
2Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445590              
3Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              

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 Abstract: The reaction FeO+ + H2 → Fe+ + H2O is a simple model for hydrogen abstraction processes in biologically important heme systems. The geometries of all relevant stationary points on the lowest sextet and quartet surfaces were optimized using several density functionals as well as the CASSCF method. The corresponding energy profiles were computed at the following levels: density functional theory using gradient-corrected, hybrid, meta, hybrid-meta, and perturbatively corrected double hybrid functionals; single-reference coupled cluster theory including up to single, double, triple, and perturbative quadruple excitations [CCSDT(Q)]; correlated multireference ab initio methods (MRCI, MRAQCC, SORCI, SORCP, MRMP2, NEVPT2, and CASPT2). The calculated energies were corrected for scalar relativistic effects, zero-point vibrational energies, and core−valence correlation effects. MRCI and SORCI energies were corrected for size-consistency errors using an a posteriori Davidson correction (+Q) leading to MRCI+Q and SORCI+Q. Comparison with the available experimental data shows that CCSDT(Q) is most accurate and can thus serve as benchmark method for this electronically challenging reaction. Among the density functionals, B3LYP performs best. In the correlated ab initio calculations with a full-valence active space, SORCI+Q yields the lowest deviations from the CCSDT(Q) reference results, with qualitatively similar energy profiles being obtained from MRCI+Q and MRAQCC. SORCI+Q benefits from the quality of the approximate average natural orbitals used in the final step of the SORCI procedure. Many of the tested methods show surprisingly large errors. The present results validate the common use of B3LYP in computational studies of heme systems and offer guidance on which correlated ab initio methods are most suitable for such studies.

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Language(s): eng - English
 Dates: 2014-06-162014-07-232014-09-09
 Publication Status: Published in print
 Pages: 14
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 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ct500522d
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Title: Journal of Chemical Theory and Computation
  Abbreviation : J. Chem. Theory Comput.
Source Genre: Journal
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Publ. Info: Washington, D.C. : American Chemical Society
Pages: - Volume / Issue: 10 (9) Sequence Number: - Start / End Page: 3807 - 3820 Identifier: ISSN: 1549-9618
CoNE: https://pure.mpg.de/cone/journals/resource/111088195283832