DFT Reactivity Descriptors and Catalysis - Vrije Universiteit Brussel

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A final comment • nowadays: increasing interest in higher order response functions ( ) ( ∂ n E ∂ m Nδ m' v r ) ( n = m + m' ) • recently the third order response function 3 ⎛ ⎞ ∂ ⎜ ⎝ ∂ ∂ E δ δη ⎟ = = ⎠ ( ) ⎟ δ ( ) ( ) f r 2 N v r v r N ∂ Dual Descriptor C.Morell, A. Grand, A.Toro-Labbé, J.Phys.Chem.A, 109, 205 (2005) turned out to yield a firm basis to regain the Woodward Hoffmann rules for pericyclic reactions, in a density – only context. avoiding the phase, sign, symmetry of the wave function (cfr. ρ(r) is strictly positive and has a trivial symmetry) F. De Proft, P.W. Ayers,S. Fias, P. Geerlings, J.Chem.Phys, 125, 214101 (2006) P.W. Ayers, C. Morell, F. De Proft, P. Geerlings, Chem. Eur. J., 13, 8240 (2007) Pag. 30-9-2008 18
Applications until now mostly on (generalized) acid base reactions - acid/base (Arrhenius, BrØnsted-Lowry) - generalized acid base (Lewis) → complexation reactions importance in Zeolite chemistry/ catalysis - organic chemistry • electrophilic/nucleopilic • substitution/addition/elimination Use of Principles - EEP (Electronegativity Equalization Principle) (Sanderson, Mortier) - HSAB (Hard and Soft Acids and Bases Principle; global/local)(Parr, Pearson) - MHP (Maximum Hardness Principle)(Pearson) Pag. 30-9-2008 19
Page 1 and 2: DFT Reactivity Descriptors and Cata
Page 3 and 4: Outline 1. Robert Schoonheydt and t
Page 5 and 6: Pag. 30-9-2008 5
Page 7 and 8: Pag. 30-9-2008 7
Page 9 and 10: Pag. 30-9-2008 9
Page 11 and 12: 2. Chemical Concepts from DFT Funda
Page 13 and 14: Conceptual DFT (R.G. Parr, W. Yang,
Page 15 and 16: Identification of two first derivat
Page 17: • Ambiguity in the definition var
Page 21 and 22: 3. Some applications of global and
Page 23 and 24: The Two Step Consecutive Mechanism
Page 25 and 26: • Rate Constant Evaluation • Tr
Page 27 and 28: • Local level • Softness indica
Page 29 and 30: 3.2 Lewis acid Catalysis: the role
Page 31 and 32: Transition States C m H 3Cb X 1 H 2
Page 33 and 34: Cyclic TS characterized by several
Page 35 and 36: 4. Towards the Inclusion of Confine
Page 37 and 38: Atoms • previous work (1992-2005)
Page 39 and 40: An atom test case: helium Radial De
Page 41 and 42: Ethylene: planar confinement • Sa
Page 43 and 44: A first try: an order of magnitude
Page 45 and 46: Epilogue: looking back at the 1979-
Page 47: 6. Acknowledgments Prof. Wilfried M

DFT Reactivity Descriptors and Catalysis - Vrije Universiteit Brussel

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