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VILLAGE : V irtual I talian L aboratory for L arge-scale A pplications in a G eographically distribuited E nvironm

VILLAGE : V irtual I talian L aboratory for L arge-scale A pplications in a G eographically distribuited E nvironment. The molecular cluster model coupled to Density Functional Theory. DV- X : Ellis et al. Chem. Phys. 1973, 2, 41,

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VILLAGE : V irtual I talian L aboratory for L arge-scale A pplications in a G eographically distribuited E nvironm

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  1. VILLAGE: Virtual Italian Laboratory for Large-scale Applications in a Geographically distribuited Environment. A.A. 2006-2007 Opportunità in Chimica

  2. A.A. 2006-2007 Opportunità in Chimica

  3. The molecular cluster model coupled to Density Functional Theory. DV-X: Ellis et al.Chem. Phys.1973, 2, 41, Ellis et al.J. Chem.Phys.1976, 65, 3629. Dmol: Delley, B. J. Chem. Phys. 1990, 92, 508, Delley, B. J. Chem. Phys. 1991, 94, 7245. ADF: Baerends et al.J. Comput. Chem. 1992, 99, 84. A.A. 2006-2007 Opportunità in Chimica

  4. Covalency: noble gas configuration; organic chemistry Lewis structures; qualitative valence bond theory. crystal field; inorganic chemistry ligand field. Molecular Orbital Theories A.A. 2006-2007 Opportunità in Chimica

  5. “Bonding is the degree of interaction between two atoms, which can be described by the amount of covalent mixing of their atomic orbital.” Solomon et al. Acc. Chem Res.2000, 33, 859 Covalency in a spectroscopic sense is related not only to metal-ligand orbital mixing ratios (the “symmetry-restricted covalency”) but also to the distortions of the metal orbitals upon bond formation (the “central-field covalence”) A.A. 2006-2007 Opportunità in Chimica

  6. Ligand K-edge X-ray absorption spectroscopy (XAS) is a new experimental probe of the covalency of a metal-ligand bond. The principal ligand K-edge XAS experiment and illustrative experimental data for [CuCl4]2-and [ZnCl4]2-. A.A. 2006-2007 Opportunità in Chimica

  7. Cl 1s * Ligand K-edge spectroscopy is a direct probe of the covalency of a metal-ligand bond. Orbital energy diagram showing the ligand pre-edge transition. A.A. 2006-2007 Opportunità in Chimica

  8. Comparison of the electric dipole intensity mechanisms for ligand K-edge transitions and optical charge transfer transitions. A.A. 2006-2007 Opportunità in Chimica

  9. M K-edge:electric dipole forbidden (but quadrupole allowed) 1sM ndM transitions M L-edge: electric dipole allowed 2pM ndM transitions L K-edge:electric dipole allowed 1sL npL transitions A.A. 2006-2007 Opportunità in Chimica

  10. Background: Spin-Orbit Energy Levels Zeeman Spin-Orbit mj = 3/2 mj = 1/2 mj = –1/2 mj = –3/2 l= 1 (p) j = 3/2 s = 1/2 mj = 1/2 mj = –1/2 j = 1/2 mj = 1/2 l= 0 (s) s = 1/2 mj = –1/2 j = 1/2 A.A. 2006-2007 Opportunità in Chimica

  11. Application of SO-RTD-DFT to closed shell complexes Ti(5-C5H5)Cl3 Ti(5-C5H5)2Cl2 TiCl4 A.A. 2006-2007 Opportunità in Chimica

  12. Ti K-edgeof TiCl4, TiCpCl3, TiCp2Cl2 DeBeer George et al. J. Am. Chem. Soc.2005, 217, 667 Kuetgens & Hormes SIF Conference Proceedings1990,25, 59 A.A. 2006-2007 Opportunità in Chimica

  13. Ti L2,3-edgeTiCl4, TiCpCl3, TiCp2Cl2 Cl K-edgeTiCl4, TiCpCl3, TiCp2Cl2 DeBeer George et al. J. Am. Chem. Soc.2005, 217, 667 Wen & Hitchcock Can. J. Chem.1993, 71, 1632 A.A. 2006-2007 Opportunità in Chimica

  14. Background: Spin-Orbit Energy Levels Zeeman Spin-Orbit mj = 3/2 mj = 1/2 mj = –1/2 mj = –3/2 l= 1 (p) j = 3/2 s = 1/2 mj = 1/2 mj = –1/2 j = 1/2 mj = 1/2 l= 0 (s) s = 1/2 mj = –1/2 j = 1/2 A.A. 2006-2007 Opportunità in Chimica

  15. Correlation diagram of TiCl4, TiCpCl3, and TiCp2Cl2 frontier orbitals A.A. 2006-2007 Opportunità in Chimica

  16. The relativistic two-component ZORA-TDDFT F. Wang et al. J. Chem. Phys.2005, 122, 204103 This method allows the calculation of excitation energies and intensities for closed shell molecules, including spin–orbit coupling and with full use of symmetry. A.A. 2006-2007 Opportunità in Chimica

  17. ZORA-TDDFT l2 = corresponds to to square of the excitation energies Theoscillator strength flcanbe exctractedfrom Fl A.A. 2006-2007 Opportunità in Chimica

  18. A.A. 2006-2007 Opportunità in Chimica

  19. A.A. 2006-2007 Opportunità in Chimica

  20. Cl K-edgeTiCl4, TiCpCl3, TiCp2Cl2 DeBeer George et al. J. Am. Chem. Soc.2005, 217, 667 A.A. 2006-2007 Opportunità in Chimica

  21. Ti L2,3-edge A.A. 2006-2007 Opportunità in Chimica

  22. FROM SILICON TO RNA: THE COMING OF AGE OF AB INITIO MOLECULAR DYNAMICS “First principle quantum mechanical calculations are by now considered a sort of new spectroscopy, being widely recognized that the chemical and structural information they provide is often more accessible and likewise reliable than that provided by conventional spectroscopies” M. Parrinello, Solid State Commun. 1997, 102,107 A.A. 2006-2007 Opportunità in Chimica

  23. “People want to change the natural into the useful unnatural” Hoffmann, R. in the Introduction to “The new chemistry” Nina Hall ed. Cambridge University Press, 2000 A.A. 2006-2007 Opportunità in Chimica

  24. Perturbations induced by dilute impurities in the electronic structure of a specific host Casarin et al J. Mol. Struct. (Theochem)2003, 631, 11 Chem. Phys. Lett.2004, 392, 146 Chem. Phys. Lett.2005, 405, 459 A.A. 2006-2007 Opportunità in Chimica

  25. Phenomena related to the coordination chemistry of surfaces Casarin et al • J. Phys. Chem. B2002, 106,795 • Inorg. Chem.2003, 42, 436 • Phys. Chem. Chem. Phys. 2003, 5, 2461 • Surf. Sci. 2004, 566, 451 • Surf. Sci. 2004, 566, 890 • J. Phys. Chem. B2005, 109,1652 • J. Phys. Chem. B2005, 109,12596 • J. Phys. Chem. B2005, 109,21766 • J. Phys. Chem. C submitted A.A. 2006-2007 Opportunità in Chimica

  26. Molecular Models of Extended Solids Casarinet al. Inorg. Chem.2004, 43, 5865 Inorg. Chem.2005, 44, 6225 Cryst. GrowthDes.2007, 7, xxx A.A. 2006-2007 Opportunità in Chimica

  27. 1s4p Cl K-edge XAS spectra of [ZnCl4]2- and D2d-[CuCl4]2-; inset shows the dx2- y2 HOMO of D4h-[CuCl4]2-. Orbital energy diagram showing the ligand pre-edge transition. A.A. 2006-2007 Opportunità in Chimica

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