slide1 n.
Download
Skip this Video
Loading SlideShow in 5 Seconds..
VILLAGE : V irtual I talian L aboratory for L arge-scale A pplications in a G eographically distribuited E nvironm PowerPoint Presentation
Download Presentation
VILLAGE : V irtual I talian L aboratory for L arge-scale A pplications in a G eographically distribuited E nvironm

Loading in 2 Seconds...

play fullscreen
1 / 27

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


  • 124 Views
  • Uploaded on

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,

loader
I am the owner, or an agent authorized to act on behalf of the owner, of the copyrighted work described.
capcha
Download Presentation

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


An Image/Link below is provided (as is) to download presentation

Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author.While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server.


- - - - - - - - - - - - - - - - - - - - - - - - - - E N D - - - - - - - - - - - - - - - - - - - - - - - - - -
Presentation Transcript
slide1

VILLAGE:

Virtual Italian Laboratory for Large-scale Applications in a Geographically distribuited Environment.

A.A. 2006-2007

Opportunità in Chimica

slide2
A.A. 2006-2007

Opportunità in Chimica

slide3

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

slide4

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

slide5

“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

slide6

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

slide7

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

slide8

Comparison of the electric dipole intensity mechanisms for ligand K-edge transitions and optical charge transfer transitions.

A.A. 2006-2007

Opportunità in Chimica

slide9

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

slide10

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

slide11

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

slide12

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

slide13

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

slide14

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

slide15

Correlation diagram of TiCl4, TiCpCl3, and TiCp2Cl2 frontier orbitals

A.A. 2006-2007

Opportunità in Chimica

slide16

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

slide17

ZORA-TDDFT

l2 = corresponds to to square of the excitation energies

Theoscillator strength flcanbe exctractedfrom Fl

A.A. 2006-2007

Opportunità in Chimica

slide18
A.A. 2006-2007

Opportunità in Chimica

slide19
A.A. 2006-2007

Opportunità in Chimica

slide20

Cl K-edgeTiCl4, TiCpCl3, TiCp2Cl2

DeBeer George et al.

J. Am. Chem. Soc.2005, 217, 667

A.A. 2006-2007

Opportunità in Chimica

slide21

Ti L2,3-edge

A.A. 2006-2007

Opportunità in Chimica

slide22

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

slide23

“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

slide24

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

slide25

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

slide26

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

slide27

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