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Int. J. Mol. Sci. 2002, 3(4), 276-309;

Chemical Reactivity as Described by Quantum Chemical Methods

Eenheid Algemene Chemie, Free University of Brussels (VUB), Pleinlaan 2,1050 Brussels,Belgium
Author to whom correspondence should be addressed.
Received: 28 September 2001 / Accepted: 7 January 2002 / Published: 25 April 2002
(This article belongs to the Special Issue Application of Density Functional Theory)
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Density Functional Theory is situated within the evolution of Quantum Chemistry as a facilitator of computations and a provider of new, chemical insights. The importance of the latter branch of DFT, conceptual DFT is highlighted following Parr's dictum "to calculate a molecule is not to understand it". An overview is given of the most important reactivity descriptors and the principles they are couched in. Examples are given on the evolution of the structure-property-wave function triangle which can be considered as the central paradigm of molecular quantum chemistry to (for many purposes) a structure-property-density triangle. Both kinetic as well as thermodynamic aspects can be included when further linking reactivity to the property vertex. In the field of organic chemistry, the ab initio calculation of functional group properties and their use in studies on acidity and basicity is discussed together with the use of DFT descriptors to study the kinetics of SN2 reactions and the regioselectivity in Diels Alder reactions. Similarity in reactivity is illustrated via a study on peptide isosteres. In the field of inorganic chemistry non empirical studies of adsorption of small molecules in zeolite cages are discussed providing Henry constants and separation constants, the latter in remarkable good agreement with experiments. Possible refinements in a conceptual DFT context are presented. Finally an example from biochemistry is discussed : the influence of point mutations on the catalytic activity of subtilisin. View Full-Text
Keywords: Conceptual DFT; Quantum Biochemistry; Zeolites; Organic Reactivity; Quantum Similarity Conceptual DFT; Quantum Biochemistry; Zeolites; Organic Reactivity; Quantum Similarity

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Geerlings, P.; De Proft, F. Chemical Reactivity as Described by Quantum Chemical Methods. Int. J. Mol. Sci. 2002, 3, 276-309.

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