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VILLAGE:
Virtual Italian Laboratory for
Large-scale Applications in a
Geographically distribuited
Environment.
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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
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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.
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Covalency:
noble gas configuration;
organic chemistry
Lewis structures;
qualitative valence bond theory.
crystal field;
inorganic chemistry
ligand field.
Molecular Orbital Theories
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“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”)
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Ligand K-edge X-ray absorption spectroscopy
(XAS) is a new experimental probe of the covalency
of a metal-ligand bond.
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The principal ligand K-edge XAS experiment and illustrative experimental data for [CuCl4]2and [ZnCl4]2-.
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

*  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.
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2
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Comparison of the electric dipole intensity mechanisms for ligand K-edge
transitions and optical charge transfer transitions.
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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
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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
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j = 1/2
mj = –1/2
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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.
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Ti K-edge of TiCl4, TiCpCl3, TiCp2Cl2
Kuetgens & Hormes
SIF Conference Proceedings 1990, 25, 59
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DeBeer George et al.
J. Am. Chem. Soc. 2005, 217, 667
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Ti L2,3-edge
TiCl4, TiCpCl3, TiCp2Cl2
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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
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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
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j = 1/2
mj = –1/2
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-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
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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.
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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  ijab a   i   2 a   i 
2
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b   j 
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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)
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4965 4945
4950
4955
4960
Excitation Energy (eV)
4965 4945
4950
4955
4960
Excitation Energy (eV)
4965
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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)
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TiCp2Cl2 (C2v)
4948
4960
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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)
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2800
2804
2808
Excitation Energy (eV)
2800
2804
2808
Excitation Energy (eV)
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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)
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470
455
460
465
Excitation Energy (eV)
470
455
460
465
Excitation Energy (eV)
470
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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
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“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
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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
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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
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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
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Molecular Models of
Extended Solids
Casarin et al.
Inorg. Chem.
2004, 43, 5865
Inorg. Chem.
2005, 44, 6225
Cryst. Growth Des. 2007, 7, xxx
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Cl K-edge XAS spectra of [ZnCl4]2- and D2d[CuCl4]2-; inset shows the dx2- y2 HOMO of D4h[CuCl4]2-.
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Orbital energy diagram showing
the ligand pre-edge transition.
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