Lecture Frank de Proft
|22 February 2012||FWN-Building 5115.0013, Nijenborgh 4, 9747 AG, Groningen|
|Speaker:||Prof. Dr. Frank de Proft|
|Affiliation:||Eenheid Algemene Chemie, Vrije Universiteit Brussel|
|Title:||Density Functional Theory based Reactivity Indices: Methodological Aspects and Applications in Organic and Inorganic Chemistry|
|Date:||Wed Feb 22, 2012|
|Telephone:||+31 50 363 7754|
Density Functional Theory is a well-suited theory for the introduction of chemical concepts, also known as reactivity indices. These are introduced as response functions of the energy E of the system with respect to either the number of electrons N, the external potential v( r ) or both. These definitions have afforded the non-empirical calculation of the reactivity indices and applications in many fields of chemistry have been studied, often combined with principles such as the electronegativity equalization principle of Sanderson and Pearson’s hard and soft acids and bases and maximum hardness principles.
In this talk, we focus on recent developments concerning methodological aspects in the computation of some of these reactivity indices, together some with recent relevant applications.
In a first part, we consider electron affinities, occurring in the evaluation of energy derivatives with respect to N. It is shown that, based upon an approximate symmetry between electron subtraction and electron addition for GGA functionals, these can be obtained using properties of only the neutral and cationic systems, thus avoiding the computation of anionic system which is often problematic, especially in the case of temporary anions. Attention will be focused on the computation of atomic electron affinities, together with the derived chemical potential and hardness. Also electron affinities of fluorinated ethylenes will be discussed.
Next, we investigate the so-called linear response function (polarizability kernel), the second derivative of the energy with respect to the external potential. In this part, we highlight the importance of this function in describing electron delocalization and show an interesting connection with the concept of aromaticity.
Finally, the Fukui function, the derivative of the electron density with respect to the number of electrons, probing the interaction of a molecule with a soft attacking reactant, is considered. We present a new, analytical procedure to evaluate this quantity . In second part, the extent of relativistic effects on the Fukui function and frontier orbital densities is analysed on the basis of three benchmark molecules containing the heavy elements Au, Pb, and Bi.
 (a) R. G. Parr and W. Yang, Density Functional Theory of Atoms and Molecules, Oxford University Press, New York, 1989. (b) R. G. Parr and W. Yang, Ann. Rev. Phys. Chem. 46, 701 (1995). (c) H. Chermette, J. Comput. Chem. 20, 129 (1999). (d) P. Geerlings, F. De Proft and W. Langenaeker, Chem. Rev. 103, 1793 (2003). (e) P. W. Ayers, J. S. M. Anderson and L. J. Bartolotti, Int. J. Quant. Chem. 101, 520 (2005).
 A. M. Teale, F. De Proft and D. J. Tozer, J. Chem. Phys. 129, 044110 (2008).
 F. De Proft, A. M. Teale, P. Geerlings and D. J. Tozer, in preparation.
 M. J. G. Peach, F. De Proft and D. J. Tozer, J. Phys. Chem. Lett. 1, 2826 (2010).
 (a) N. Sablon, F. De Proft and P. Geerlings, J. Phys. Chem. Lett. 1, 1228 (2010). (b) N. Sablon, F. De Proft and P. Geerlings, Chem. Phys. Lett. 498, 192 (2010). (c) N. Sablon, F. De Proft, P. W. Ayers and P. Geerlings J. Chem. Theory Comput. 6, 3671 (2010). (d) N. Sablon, F. De Proft, M. Solà and P. Geerlings, Phys. Chem. Chem. Phys., in press.
 W. Yang, A. J. Cohen, F. De Proft and P. Geerlings, submitted.
 N. Sablon, R. Mastalerz, F. De Proft, P. Geerlings and M. Reiher, Theor. Chem. Acc. 127, 195 (2010).
|Last modified:||22 October 2012 2.30 p.m.|