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PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
NanoBio Spectroscopy Group and ETSF Scientific Development CentreDpto. Física de Materiales, Universidad del País Vasco,
Centro Física de Materiales CSIC-UPV/EHU San Sebastián, Spainand
FHI Max-Planck-Gesellschaft, Berlin, Germany
http://nano-bio.ehu.es E-mail: [email protected]
Angel Rubio
Perspectives
“How Exciting Hands-on workshop on Excitations 2012”
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Towards atomic scale technologies: bottom-up approach
● Molecular electronics; Moore's law—---beyond Moore
● quantum information; communication
● photonic materials (holes) (“metamaterials”)
● Composite materials
● Alternative energies (photovoltaic, fuel cells, etc...)
self-assembly supramolecular chemistry
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Small is different: atoms and molecules as our building blocks
nano, bio and material science
More is different: emergent properties of matter
Computational Science: insight into the fields of Physics, Chemistry, Materials Science, Medicine, Biology, Astrophysics, Earth science, Energy, transportation, Domotics, ........
NEW CONCEPTS
Nanoelectronics + Nanoptics + Nanophononics
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Small is different: atoms and molecules as our building blocks
NEW CONCEPTS
Nanoelectronics + Nanoptics + Nanophononics
Economist, May2003
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Nanotubos de carbono: transporte de masa
B.C. Regan et al, Nature 428, 924 (2004)
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Why Theoretical Spectroscopy?
“Excitations”
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Small is different: atoms and molecules as our building blocks
More is different: emergent properties of matter
*** time resolved spectroscopy (new basic and technological concepts): eg. attosecond dynamics (Free-electron lasers) (quantum control)
NEW CONCEPTS
Nanoelectronics + Nanoptics + Nanophononics
Interrogating Molecules? (Nature)
Science, Nov. 2008 …........... and get an answer !!!
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Dark Structures in Molecular Radiationless Transitions Determined by Ultrafast Diffraction, Science, Vol 307, 558-563 (2005)
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Qbit-control
Leds and laser diodsefficiency
***Seeing is believing*****
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
***Seeing is believing*****
if you understand what you see!!!
� � � � �m
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Back to the ground
“How Exciting! Hands-on Workshop on excitations”
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Science 321, 800 -803 (2008)
Methods for various materials properties
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Time and size scales
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
DFT Success “~chemical accuracy”
Structural properties, stability, phononsPhase transitions Surface catalysis and chemical reactivityBiomodeling .................
Allows large scale simulations BUT.....
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
........present XC-functionals usually fail in describing:
LEVEL ALIGNMENT (KS): DFT-Gap
Long-range potential (atom/molecule)
Dispersion forces VdW, Solvation
Charge-transfer, multiple excitations
Memory effects; Dissipation; lifetime; de-coherence
Open shell systems and Open quantum systems
Correlated Materials ...............
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
LEVEL ALIGNMENT, Dispersion forces VdW
Aromatic molecules on
Cu(110)
N. Atodiresei, S.Blugel et al, PRL 102, 136809 (2009)
See the talk of P. Rinke for CO on surfaces
Supramolecular chemistry
Biophysics ..........
Molecular Transport
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
LEVEL ALIGNMENT, Dispersion forces VdWCharge Transfer excitationsPhotovoltaic Hybrids: Grätzell
cells
Road to Improving Efficiency: Controlling position of the frontier orbitals
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
4
5
6
7
8
9
10
11
Vac
uum
NaC
l(001
)
MgO
(001
)
CaO
(001
)
BaO
(001
)
TiO
2(00
1)
Gra
phite
Al(1
11)
Pt(
111)
Rh(
111)
Ti(0
01)
Li(0
01)
BaO
(11
1)
HO
MO
-LU
MO
Ga
p (
eV
)
GW
LDA
4
5
6
7
8
9
10
11
Vac
uum
NaC
l(001
)
MgO
(001
)
CaO
(001
)
BaO
(001
)
TiO
2(00
1)
Gra
phite
Al(1
11)
Pt(
111)
Rh(
111)
Ti(0
01)
Li(0
01)
BaO
(11
1)
HO
MO
-LU
MO
Ga
p (
eV
)
PBE0
LDA
LDA gaps are independent of substrate and distance
Same result with other functionals (GGA, hybrid or exact exchange)
GW gaps show large variation across different surfaces
GW gap sensitive to atomistic details screening is very important
The CT process at interfaces is a dynamical one
Illustrative Example: physisorbed benzene
4
5
6
7
8
9
10
11
Vac
uum
NaC
l(001
)
MgO
(001
)
CaO
(001
)
BaO
(001
)
TiO
2(00
1)
Gra
phite
Al(1
11)
Pt(
111)
Rh(
111)
Ti(0
01)
Li(0
01)
BaO
(11
1)
HO
MO
-LU
MO
Ga
p (
eV
)
GW
LDA
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Correlated materials
Sensitivity
Emergence
Phase transitions with pressure doping or temperature
Interface between correlated oxide insulators? It is metallic!
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
What is correlations and when a system is to be considered correlated? ...beyond LDA ? … beyond HF?
How much of the “model hamiltonian” studies can be captured by present “advanced” functionals
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Correlation
SIMPLE MODEL SYSTEMS
How to understand H2
and H-chain
(Mott insulator in DFT)
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
The step in KS potential
Early work of Perdew, Almbladh& von Barth, Gritsenko & Baerends Recent work of Tempel, Martinez, Maitra, JCTC (2009) and N. Helbig, I. Tokatly, A. Rubio, JCP (2009)
●Step aligns the atomic HOMOs ●Kohn-Sham system builds a ”wall“ to mimick the repulsion due to interaction and prevent tunneling
Prevents dissociation to unphysical fractional charges●Step-height = difference between highest eigenvalues of the two wells
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
VK
S- V
ion
icH-chain Mott insulator: in DFT !!!
Clearly all local functionals and most orbital dependent functionals do not capture the step in the potential
The KS systems is metallic : fxc responsible for the gap
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Open question
How to incorporate/model this efect into static and time-dependent DFT ?
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
(Some) Open questions
* Tunneling and/or CT processes at interfaces ??? Open questions
* Related concepts: * Molecular dissociation: bumps in Vxc * Electron tunneling * Rabi Oscillations
* Dissipation; lifetimes; de-coherence, Non adiabatic couplings
* Quantum control and open quantum systems
Work to be done: “new spatial and frequency-dependent functionals”
.
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Some active ? Fields for first principles modeling ??
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
The Problem with Determining Atomic Structure at the Nanoscale
Science 27 April 2007 316: 561-565
Examples of nanostructured materials. (A) Nanostructured bulk materials. (B) Intercalated mesoporous materials. (C) Discrete nanoparticles. In each case, ball-and-stick renditions of possible
structures are shown on the top, and TEM images of examples are shown on the bottom.
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
J.Phys.Chem.B 108, 9646, (2004)
Electron transfer processes in molecular devices
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Excited-state properties of confined water as it permeates through nanochannels: Nanosolvation
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Azobenzene: spectroscopy along femtosecond laser induced photoisomerization
S. Spörlein et al, Proc. Natl. Acad. Sci., 99, 7998 (2002)
HOMO
LUMO
T. Hugel et al, Science, 296, 1103 (2002) Y. Yu et al, Nature 425, 145 82003)
Azobenzene dyes are known to isomerize at the central N-N bond within fractions of picoseconds at high quantum yield [T. Nägele et al, Chem. Phys. Lett. 272, 489 (1997)].
Single-Molecule Optomechanical Cycle
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Fuel cellsGrätzel cellsphotovoltaics
ENERGY APPLICATIONS
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Towards the color of plants: e.g. Spinach
Fleming et al Nature (2005),.... (Berkeley)
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Excitations in bio-systems: encouraging results!!Green fluorescent protein and their mutants (2008, Nobel prize in Chemistry)
(Aequorea victoria: jellyfi sh)
M.A.L Marques, X. Lopez, D. Varsano, A. Castro, and A. R. Phys. Rev. Lett. 90, 158101 (2003)
Some biophysical processes
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Quantum control
R. J. Levis et al, Science 292, 709 (2001)
Time resolved pump-probe techniques
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Optimal control theory
Key question: What is the laser pulse that drives the system intoa predefi ned goal?
Procedure: Defi ne a target operator Ô and at the end of thelaser interaction (t = T) maximize the functional
W. Zhu, J. Botina, H. Rabitz, JCP 108, 1953 (1998)
Ô = |Φ > <Φ |F F target state
Example: High harmonic generation and selective bond-breaking
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Tailoring HHGHHG consists of the emission of integer multiples of the carrier frequency of a driving laser, due to its highly non-linear interaction with matter. It can be explained with the so-called 3-steps model:
Typically, the HH spectrum (emission intensity vs. photon frequency) consists of a rapid intensity decrease, a plateau, and a cut-off.
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Tailoring HHG
Tailoring femtosecond light pulses in the IR-UV regime permits to access molecular vibrations, and therefore control chemical reactions.
The natural time scale of the electrons is, however, in the attosecond regime. In order to control electrons, we need sources with XUV energies and attosecond pulse durations.
HHG is viewed as a possible source of coherent radiation in the XUV and soft X-ray regime.
HHG permits to produce trains of attosecond-length pulses.
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Tailoring HHG
7th 13th
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
The combination of MBPT and (TD)DFT is a powerful tool to “predictive” describe the combined
dynamics of electron/ion in response to external electromagnetic fields of large scale nanostructures, biological molecules and extended systems spanning
very different time scales
ETSF
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
It is one of the frst duties of a professor, for example, in any
subject, to exaggerate a little both the importance of his subject and
his own importance in it
G. H. Hardy (1940). A Mathematician's Apology.
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Nanotechnology: a higher form of evolution? (Humility is perhaps appropriate…)
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Than
k yo
u!!!!
For more details see:http://nano-bio.ehu.eshttp://etsf.eu
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
Acknowledgements
N. Helbig, J. Fuks, A. Crawford, J.Walkenhorst, L. Stella, I. Tokatly, S. Kurth
ETSF , Dpto Material Physics, Centro Mixto CSIC-UPV, Donostia, Spain
E. K. U. Gross MPI-Halle
N. Maitra Hunter College NY C.A. Rozzi
A. Castro BIFI, Zaragoza H. Appel FHI-Berlin
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
K. Kriger, A. Castro, E.K.U. Gross, (unpublished)
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007
PerspectivesHoW exciting! Hands-on Workshop on Excitations 2012. HU Berlin, August 2-8, 2012
Workshop “Non adiabati
c dynamic
s at surfaces
”, Schloss Reisens
burg October
2007
12th Density Functional Theory Conference, Amsterdam, August 2007