ETS-NOCV-ADF.ppt

Applications of ETS-NOCV method in description of various types of chemical bonds Mariusz P. Mitoraj Jagiellonian University Cracow, Poland Department of Theoretical Chemistry ADF webinar, Kraków-rest-of-the-world, 28th Feb., 2014 Examples of theoretical quantities for visualization of chemical bond ADF webinar, Kraków-restoftheworld, 28th Feb., 2014 Formation of chemical bond in H2 – ?? based picture H H ?H2 Deformation density (Differential density) (1) qualitative data by inspection of the sign of ??: negative (outflow), positive (inflow) of density due to bond formation H H 1. Start from promolecular state (atom/fragments) ?H=1s2 ?H=1s2 ADF webinar, Kraków-restoftheworld, 28th Feb., 2014 The Natural Orbitals for Chemical Valence (NOCV) NOCV’s also decompose the deformation density ??: useful qualitative data by inspection of the sign of ??: negative (outflow), positive (inflow) of density Mitoraj, M.; Michalak, A. Organometallics 2007, 26(26); 6576., Michalak, A.; Mitoraj, M.; Ziegler, T. J. Phys. Chem. A. 2008, 112 (9), 1933, Mitoraj, M.; Michalak, A. J. Mol. Model., 2008, 14, 681, Mitoraj, M.; Zhu, H.; Michalak, A.; Ziegler, T. 2008, International Journal of Quantum Chemistry, DOI: 10.1002/qua.21910., Mitoraj, M.; Michalak, A. J. Mol. Model. 2008, 14, 681. NOCV’s ( ) diagonalize the deformation density matrix: where ?P=P-P0 , density matrix of the combined molecule, P0- density matrix of the considered molecular fragments. NOCV’s are in pairs: Radoń, M. Theor Chem Account 2008, 120,337. back donation donation back donation The contours of the deformation density (??) and the contributions from the pairs of complementary orbitals for the heme/CO system ?q? = 0.74 ?q? = 1.04 -De=?Etotal= ?Edist + ?Eelstat + ?EPauli + ?Eorb ETS: Energetic estimation of ??k A combination of ETS and NOCV - (ETS-NOCV) NOCV: ETS-NOCV: Mariusz P. Mitoraj, Artur Michalak and Tom Ziegler ?A combined charge and energy decom- Position schem