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Molecular acidity: A quantitative conceptual density functional theory description

J. Chem. Phys. 131, 164107 (2009); doi:10.1063/1.3251124

Published 23 October 2009

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Shubin Liu,1 Cynthia K. Schauer,2 and Lee G. Pedersen2,3
1Research Computing Center, University of North Carolina, Chapel Hill, North Carolina 27599-3420, USA
2Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599-3290, USA
3Laboratory of Structural Biology, National Institute of Environmental Health Sciences, Research Triangle Park, P.O. Box 12233, North Carolina 27709, USA
Accurate predictions of molecular acidity using ab initio and density functional approaches are still a daunting task. Using electronic and reactivity properties, one can quantitatively estimate pKa values of acids. In a recent paper [S. B. Liu and L. G. Pedersen, J. Phys. Chem. A 113, 3648 (2009)], we employed the molecular electrostatic potential (MEP) on the nucleus and the sum of valence natural atomic orbital (NAO) energies for the purpose. In this work, we reformulate these relationships on the basis of conceptual density functional theory and compare the results with those from the thermodynamic cycle method. We show that MEP and NAO properties of the dissociating proton of an acid should satisfy the same relationships with experimental pKa data. We employ 27 main groups and first to third row transition metal-water complexes as illustrative examples to numerically verify the validity of these strong linear correlations. Results also show that the accuracy of our approach and that of the conventional method through the thermodynamic cycle are statistically similar. ©2009 American Institute of Physics
History: Received 19 July 2009; accepted 30 September 2009; published 23 October 2009
Permalink: http://link.aip.org/link/?JCPSA6/131/164107/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.30.Lp
    Decomposition chemical reactions (pyrolysis, dissociation, and fragmentation)
  • 82.20.Ej
    Quantum theory of reaction cross section in chemical kinetics
  • 82.60.Hc
    Chemical equilibria and equilibrium constants
  • YEAR: 2009

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ISSN:
0021-9606 (print)   1089-7690 (online)
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