Physical nature of interactions in ZnII complexes with 2,2′-bipyridyl : quantum theory of atoms in molecules (QTAIM), interacting quantum atoms (IQA), noncovalent interactions (NCI), and extended transition state coupled with natural orbitals for chemical valence (ETS-NOCV) comparative studies

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dc.contributor.author Cukrowski, Ignacy
dc.contributor.author De Lange, Jurgens Hendrik
dc.contributor.author Mitoraj, Mariusz
dc.date.accessioned 2015-08-03T11:01:02Z
dc.date.available 2015-08-03T11:01:02Z
dc.date.issued 2014-01
dc.description.abstract In the present account factors determining the stability of ZnL, ZnL2, ZnL3 complexes (L = bpy, 2,2-bipyridyl) were characterized based on various techniques: the Quantum Theory of Atoms in Molecules (QTAIM), energy decomposition schemes based on Interacting Quantum Atoms (IQA) and Extended Transition State coupled with Natural Orbitals for Chemical Valence (ETSNOCV). Finally, the Non-covalent Interactions (NCI) index was also applied. All methods consistently indicated that the strength of the coordination bonds, Zn–O, Zn–N, decreases from ZnL to ZnL3. Importantly, it has been identified that the strength of secondary intramolecular heteropolar hydrogen bonding interactions, CH•••O, CH•••N, increases when going from ZnL to ZnL3. A similar trend appeared to be valid for the π -bonding as well as electrostatic stabilization. In addition to the above leading bonding contributions, all techniques suggested the existence of very subtle, but non-negligible additional stabilization from the CH•••HC electronic exchange channel; these interactions are the weakest among all considered here. From IQA it was found that the local diatomic interaction energy, H,H int E , amounts at HF to –2.5, –2.7 and –2.9 kcal mol–1 for ZnL, ZnL2 and ZnL3, respectively (–2.1 kcal mol–1 for ZnL at MP2). NOCV-based deformation density channels showed that formation of CH--HC contacts in Zn-complexes causes significant polarization of (C–H) bonds, which accordingly leads to charge accumulation in the CH•••HC bay region. Charge depletion from (C–H) bonds were also reflected in the calculated spin-spin 1J(C–H) coupling constants, which decrease from 177.06 Hz (ZnL) to 173.87 Hz (ZnL3). This last result supports our findings of an increase in the local electronic CH•••HC stabilization from ZnL to ZnL3 found from QTAIM, IQA, and ETS-NOCV. Finally, this work unites for the first time the results from four methods that are widely used for description of chemical bonding. en_ZA
dc.description.librarian hb2015 en_ZA
dc.description.sponsorship University of Pretoria, National Research Foundation, Polish Ministry of Science and Higher Education (“Outstanding Young Researchers” scholarships, 2010, 2011−2014 and young researchers T-subsidy) and from the National Science Center in Poland (grant N N204 198040). en_ZA
dc.description.uri http://pubs.acs.org/journal/jpcafh en_ZA
dc.identifier.citation Cukrowski, I, De Lange, JH & Mitoraj, M 2014, 'Physical nature of interactions in ZnII complexes with 2,2′-bipyridyl : quantum theory of atoms in molecules (QTAIM), interacting quantum atoms (IQA), noncovalent interactions (NCI), and extended transition state coupled with natural orbitals for chemical valence (ETS-NOCV) comparative studies', Journal of Physical Chemistry A, vol. 118, no. 3, pp. 623-637. en_ZA
dc.identifier.issn 1089-5639 (print)
dc.identifier.issn 1520-5215 (online)
dc.identifier.other 10.1021/jp410744x
dc.identifier.uri http://hdl.handle.net/2263/49240
dc.language.iso en en_ZA
dc.publisher American Chemical Society en_ZA
dc.rights This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry A, © 2014 American Chemical Society after peer review and technical editing by the publisher. en_ZA
dc.subject Energy partitioning en_ZA
dc.subject Zinc en_ZA
dc.subject Bipyridyl en_ZA
dc.subject CH–O bond en_ZA
dc.subject CH–N bond en_ZA
dc.subject CH–HC interaction en_ZA
dc.subject Quantum theory of atoms in molecules (QTAIM) en_ZA
dc.subject Interacting quantum atoms (IQA) en_ZA
dc.subject Noncovalent interactions (NCI) en_ZA
dc.subject Extended transition state coupled with natural orbitals for chemical valence (ETS-NOCV) en_ZA
dc.subject Density functional theory (DFT) en_ZA
dc.title Physical nature of interactions in ZnII complexes with 2,2′-bipyridyl : quantum theory of atoms in molecules (QTAIM), interacting quantum atoms (IQA), noncovalent interactions (NCI), and extended transition state coupled with natural orbitals for chemical valence (ETS-NOCV) comparative studies en_ZA
dc.type Postprint Article en_ZA


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