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Performance of DFT in modeling electronic and structural properties of cobalamins
Author(s) -
Kuta Jadwiga,
Patchkovskii Seguei,
Zgierski Marek Z.,
Kozlowski Pawel M.
Publication year - 2006
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20454
Subject(s) - bond length , density functional theory , bond dissociation energy , bond strength , bond , computational chemistry , dissociation (chemistry) , chemistry , materials science , electronic structure , molecule , nanotechnology , organic chemistry , adhesive , layer (electronics) , finance , economics
Computational modeling of the enzymatic activity of B 12 ‐dependent enzymes requires a detailed understanding of the factors that influence the strength of the CoC bond and the limits associated with a particular level of theory. To address this issue, a systematic analysis of the electronic and structural properties of coenzyme B 12 models has been performed to establish the performance of three different functionals including B3LYP, BP86, and revPBE. In particular the cobalt–carbon bond dissociation energies, axial bond lengths, and selected stretching frequencies have been analyzed in detail. Current analysis shows that widely used B3LYP functional significantly underestimates the strength of the CoC bond while the nonhybrid BP86 functional produces very consistent results in comparison to experimental data. To explain such different performance of these functionals molecular orbital analysis associated with axial bonds has been performed to show differences in axial bonding provided by hybrid and nonhybrid functionals. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 1429–1437, 2006