QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. VILLAGE: Virtual Italian Laboratory for Large-scale Applications in a Geographically distribuited Environment. A.A. 2006-2007 Opportunità in Chimica QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. A.A. 2006-2007 Opportunità in Chimica Agnoli Stefano Armelao Lidia Barreca Davide Bottaro Gregorio Casarin Maurizio Correzzola Claudio El Habra Naida Forrer Daniel Garau Federica Gasparotto Alberto Glisenti Antonella Granozzi Gaetano Gross Silvia Maccato Chiara Orzali Tommaso Pandolfo Luciano Sambi Mauro Sedona Francesco Tondello Eugenio Vittadini Andrea University of Padova CNR of Padova CNR of Padova CNR of Padova University of Padova University of Padova University of Padova University of Padova University of Padova University of Padova University of Padova University of Padova CNR of Padova University of Padova University of Padova University of Padova University of Padova University of Padova University of Padova CNR of Padova Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. The molecular cluster model coupled to Density Functional Theory. DV-X: Dmol: ADF: Ellis et al. Chem. Phys. 1973, 2, 41, Ellis et al. J. Chem. Phys. 1976, 65, 3629. Delley, B. J. Chem. Phys. 1990, 92, 508, Delley, B. J. Chem. Phys. 1991, 94, 7245. Baerends et al. J. Comput. Chem. 1992, 99, 84. A.A. 2006-2007 Opportunità in Chimica Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. 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 Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. “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 Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. Ligand K-edge X-ray absorption spectroscopy (XAS) is a new experimental probe of the covalency of a metal-ligand bond. QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. The principal ligand K-edge XAS experiment and illustrative experimental data for [CuCl4]2and [ZnCl4]2-. A.A. 2006-2007 Opportunità in Chimica Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. * 1 2 Cu 3dx2 -y2 Cl 3p Int Cl 1s * const Cl 1s r * 2 2 const Cl 1s r Cl 3p 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 Padova - 05/04/07 2 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. Comparison of the electric dipole intensity mechanisms for ligand K-edge transitions and optical charge transfer transitions. A.A. 2006-2007 Opportunità in Chimica Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. 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 Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. Background: Spin-Orbit Energy Levels Spin-Orbit Zeeman 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 A.A. 2006-2007 Opportunità in Chimica j = 1/2 mj = –1/2 Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. Application of SO-RTD-DFT to closed shell complexes TiCl4 Ti(5-C5H5)Cl3 Ti(5-C5H5)2Cl2 The interest for this complexes has to be ultimately traced back to two factors: i) the catalytic activity of both mono- and biscyclopentadienyl titanium(IV) complexes; ii) the possible use of titanocene dichloride and its water soluble derivatives as possible alternatives to t he widely used heavy metal based anticancer drugs. A.A. 2006-2007 Opportunità in Chimica Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. Ti K-edge of TiCl4, TiCpCl3, TiCp2Cl2 Kuetgens & Hormes SIF Conference Proceedings 1990, 25, 59 A.A. 2006-2007 Opportunità in Chimica DeBeer George et al. J. Am. Chem. Soc. 2005, 217, 667 Padova - 05/04/07 Ti L2,3-edge TiCl4, TiCpCl3, TiCp2Cl2 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. Cl K-edge TiCl4, 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 Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. Background: Spin-Orbit Energy Levels Spin-Orbit Zeeman 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 A.A. 2006-2007 Opportunità in Chimica j = 1/2 mj = –1/2 Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. -2 37a' 22a" -3 36a' -4 Energy (eV) 10t2 -5 25a1 10a2 17b1 16b2 24a1 21a"+35a' 3e -6 15b2 -7 20a"+34a' -8 2t1 -9 TiCl4 (T d) TiCpCl3 (Cs) TiCp2Cl2 (C2v) Correlation diagram of TiCl4, TiCpCl3, and TiCp2Cl2 frontier orbitals A.A. 2006-2007 Opportunità in Chimica Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. 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 Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. ZORA-TDDFT F 2F l2 = corresponds to to square of the excitation energies The oscillator strength fl can be exctracted from Fl Fia Pjb ia , jb ijab a i 2 a i 2 A.A. 2006-2007 Opportunità in Chimica b j Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. TiCl4 f (oscillator strength) 1.5x10 t2 a' a" TiCpCl3 -3 TiCp 2Cl2 a1 b1 b2 Y 1.0 X 0.5 X X' X X' 0.0 4945 4950 4955 4960 Excitation Energy (eV) A.A. 2006-2007 Opportunità in Chimica 4965 4945 4950 4955 4960 Excitation Energy (eV) 4965 4945 4950 4955 4960 Excitation Energy (eV) 4965 Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. 1.0x10 37a' 22a" -3 36a' -4 Energy (eV) 10t2 -5 25a1 10a2 17b1 16b2 0.8 24a1 21a"+35a' 3e -6 15b2 20a"+34a' z t 0.6 y y" 0.4 x' -7 TiCl4 TiCpCl3 TiCp2Cl2 x f (oscillator strength) -2 -3 x" 0.2 y y' x' x" 4950 4952 4954 4956 4958 Excitation Energy (eV) -8 0.0 2t1 -9 TiCl4 (T d) TiCpCl3 (Cs) A.A. 2006-2007 Opportunità in Chimica TiCp2Cl2 (C2v) 4948 4960 Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. Cl K-edge TiCl4, TiCpCl3, TiCp2Cl2 DeBeer George et al. J. Am. Chem. Soc. 2005, 217, 667 3.0x10 -3 f (oscillator strength) 2.5 X TiCl4 a' a" X' TiCpCl3 X" 2.0 X" a1 b1 b2 TiCp2Cl2 X' 1.5 1.0 0.5 0.0 2800 2804 2808 Excitation Energy (eV) A.A. 2006-2007 Opportunità in Chimica 2800 2804 2808 Excitation Energy (eV) 2800 2804 2808 Excitation Energy (eV) Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. Ti L2,3-edge 0.30 X' X' 0.25 f (oscillator strength) a' a" T iCl4 2p3/2 2p3/2 2p1/2 0.15 0.10 a1 b1 b2 Y' Y' 0.20 X' T iCpCl3 2p1/2 T iCp2Cl2 Y' 2p3/2 2p1/2 S X Y" Y X X" Y" X 0.05 0.00 455 460 465 Excitation Energy (eV) A.A. 2006-2007 Opportunità in Chimica 470 455 460 465 Excitation Energy (eV) 470 455 460 465 Excitation Energy (eV) 470 Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. 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 Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. “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 Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. 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 Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. Phenomena related to the coordination chemistry of surfaces Casarin et al J. Phys. Chem. B Inorg. Chem. Phys. Chem. Chem. Phys. Surf. Sci. Surf. Sci. J. Phys. Chem. B J. Phys. Chem. B J. Phys. Chem. B J. Phys. Chem. C A.A. 2006-2007 Opportunità in Chimica 2002, 106, 795 2003, 42, 436 2003, 5, 2461 2004, 566, 451 2004, 566, 890 2005, 109, 1652 2005, 109, 12596 2005, 109, 21766 submitted Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. Molecular Models of Extended Solids Casarin et al. Inorg. Chem. 2004, 43, 5865 Inorg. Chem. 2005, 44, 6225 Cryst. Growth Des. 2007, 7, xxx A.A. 2006-2007 Opportunità in Chimica Padova - 05/04/07 QuickTime™ and a TIFF (LZW) decompressor are needed to see this picture. Cl K-edge XAS spectra of [ZnCl4]2- and D2d[CuCl4]2-; inset shows the dx2- y2 HOMO of D4h[CuCl4]2-. A.A. 2006-2007 Opportunità in Chimica Orbital energy diagram showing the ligand pre-edge transition. Padova - 05/04/07