Theoretical studies of the reductive C-S bond cleavage in complexes of the form [M(9S3)2]2+ (M = Re, Tc, and Ru; 9S3 = 1,4,7-Trithiacyclononane)

Journal of Physical Chemistry A

Volumn 108, Issue 52, 2004, Pages 11494-11499

  Maurer, Patrick ^a,b   Magistrato, Alessandra ^a,c   Rothlisberger, Ursula ^a,b  

^a LABORATORY OF INORGANIC CHEMISTRY   (Switzerland)

^b EPFL   (Switzerland)

^c DEMOCRITOS NATIONAL SIMULATION CENTER   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ENERGY; CARBON; CORRELATION METHODS; ELECTRIC CHARGE; ORBITAL TRANSFER; RADIATION; RHENIUM; SULFUR;

BIOLOGICAL FUNCTIONS; DENSITY FUNCTIONAL THEORY (DFT); GENERALIZED GRADIENT APPROXIMATION (GGA); TRANSITION METAL ELEMENTS;

BONDING;

EID: 11344269745     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp045615n     Document Type: Article

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28. This value (smaller than the dissociation limit) corresponds to a marginal barrier for dissociating ethene from the reactant. This barrier could also be an artifact arising from the choice of the constraint coordinate, or from the known difficulties of DFT in describing dissociation of molecules with an uneven number of electrons (see for example, Zhang, Y.; Yang, W. J. Chem. Phys. 1998, 109, 2604; Becke, A. D. J. Chem. Phys. 2003, 119, 2972).
29. This value (smaller than the dissociation limit) corresponds to a marginal barrier for dissociating ethene from the reactant. This barrier could also be an artifact arising from the choice of the constraint coordinate, or from the known difficulties of DFT in describing dissociation of molecules with an uneven number of electrons (see for example, Zhang, Y.; Yang, W. J. Chem. Phys. 1998, 109, 2604; Becke, A. D. J. Chem. Phys. 2003, 119, 2972).
30. Calculations with atom-centered basis functions yield reaction energies that agree with the values in Table 2 within 2 kcal/mol, which confirms that the energetic differences indeed result from the correlation energy functionals, and not, for example, from the use of pseudopotentials. These calculations were carried out with the programm ADF2003.01 (te Velde, G. et al. J. Comput. Chem. 2001, 22, 931), using the builtin TZ2P basis set (triple-ζ + two polarization functions) and the ZORA relativistic approximation.