1. EURONanochem; Chemical Control at the Nanoscale

2. EURONanochem Eurocore proposal co-ordinated by Professor G Dujardin
Laboratoire de Photophysique Moléculaire, Université de ParisXI,FRANCE
Professor G Gerber
Fakultät für Physik und Astronomie, Universität Würzburg,GERMANY
Professor F Gianturco
Department of Chemistry; Università di Roma "La Sapienza; ITALY
Professor Nigel J Mason (co-ordinator)
Department of Physics & Astronomy, Open University, UNITED KINGDOM
Professor T D Maerk
Institut Ionenphysik, University of Innsbruck, AUSTRIA

3. EURONanochem Problem:
Conventional chemical reactions are mainly controlled
based on conventional termodynamic variables.
Aim:
To control chemical reactions through the ability to
select the pathways of molecular dissociation.
Methodology;
Control using photodissociation;
Control using electron induced fragmentation;
Provide spatial control through STM

4. EURONanochem Brief description:
Chemical control with photons; Using laser pulses with a duration of femtoseconds/picoseconds, the timescale on which the atoms in a molecule move, to manipulate molecular wavepackets and control dissociation pathways
Chemical control using very low energy electrons to dissociate the molecular target at well defined reaction sites
The application of STM technology to electron induced manipulation of single molecules on surfaces

5. Bond Selectivity using photons Process of “coherent control”.
Exploits the optical phase of coherent laser light, coined “coherent control”. Such techniques employ quantum mechanical interference between the pathways leading to products of a chemical reaction.
One fs laser pulse can induce the molecule only to bend, while a different light pulse will cause it only to stretch. Hence can select specific vibrations in molecules leading to specific bond ruptures in turn opening possibility of controlling chemical reactions.

6. Optical control
Electric control field E(t)

7. A laser-controlled molecule
Fully automated control
Science 282, 919 (1998)
cited >500

8. Optimal Control Experiments
molecular gas phase photodissociation
(selective bond-cleavage)
selective excitation of complex molecules
in the liquid phase
photoisomerization of complex molecules
selective bond-forming reactions

9. selectivity?
selectivity?
Bond Cleavage
Bond Formation
Femtosecond Laser-Assisted Catalytic Surface Reactions of Syngas (CO+H2) and their Optimization by Tailored Laser Pulses,
Gerber et al., Wuerzburg

10. EURONanochem: The programme
Topic 1; Chemical Control using light Develop ultrafast femtosecond chemistry for selective bond by
developing automated optimization of branching ratios of gas phase photodissociation reactions
develop the technique of femtosecond polarization pulse shaping to study the attachment of functional groups to surfaces of materials such as semiconductors or molecular self-assembled monolayers;
extending present studies into the liquid phase to explore more biologically relevant chemical processes and
complementing these experiments by theoretical studies.

11. Bond Selectivity using Electrons
Process of Dissociative Electron Attachment (Low electron energy!!!)

12. Electron Induced Chemistry; Chemical Control at the Molecular Level
Selective C-Cl bond
cleavage at 0 eV
Selective C-F bond
cleavage at 3.2 eV

13. Low-energy electrons induce single- and double-strand breaks in DNA
An electron initially binds to DNA forming transient molecular anion. This anion transforms in a sequence of processes, leading to DNA strand breaks.

14. Example of Chemical surface transformations
DEA produces products that subsequently react on the surface
E.g. Irradiate film of NF3 and CH3Cl
Form CH3F e- e-
CH3Cl
no ions
Cl- e-
(NF3)n•(CH3Cl)m F-

15. e-
Cl- F-
CH3F
CH3Cl

16. Control via e--induced chemistry developing electron lithography
Basic
e--molecule
interactions
Resonances
E0 dependence
e--induced chemistry
Cross sections
Typical reactions and products
Reaction sequences
Surface functionalization
Reactions at the interface of materials
Modification of materials properties
- structural - electrical
- permeability
- optical

17. EURONanochem: The programme
Topic 2; Chemical Control using electrons
to study intermolecular reactions leading to controlled coupling of a reactive fragment to another material
to study the attachment of functional groups to surfaces of materials such as semiconductors or molecular self-assembled monolayers;
to explore the potential of these reactions for chemical lithography and e-beam techniques and
to guide these experiments by theoretical studies, i.e. to predict which of different possible intermolecular reactions is energetically the most likely.

18. Chemical control using STM
Nature, 2003

19. STM induced chemistry

20. Sloan and Palmer Nature 434, Electron excitation and dissociation of individual oriented chlorobenzene molecules on a Si(111)-7 7 surface
The first electron interacts with the chlorobenzene molecule; the molecule is left vibrationally excited (specifically, the C−Cl wag mode is excited); the second electron interacts with the molecule before the C−Cl wag mode has fully relaxed, leading to dissociation of the C−Cl bond by DEA;

21. EURONanochem: The programme
Topic 3; Chemical Control on the nanoscale
STM experiments on prototype organic molecules adsorbed on surfaces with the aim of fabricating complex molecular architectures of any desired shape and size on the surface.
Electron Simulated Desorption (ESD) and High Resolution Electron Energy Loss Spectroscopy (HREELS) experiments on to identify the ion resonances and the electronic transitions involved in the excitation mechanisms as well as the final products of the molecular reactions.
Development of a comprehensive simulation of the coupled surface and STM tip system to model excitation and bond breaking of single molecules by STM-IET.
Molecular dynamical calculations to unravel details of atomic and molecular manipulation at surfaces, leading to lateral motion, bond making or breaking, and desorption of the adsorbates.

22. EURONanochem: The programme
Exploitation:
To explore how such fundamental techniques may be developed as a commercially viable technique.
In developing such chemical control we also wish to exploit it in other modern technologies such as quantum information, nanotechnology and the biosciences.

23. EURONanochem: The programme
Organisational
Establishment of a European forum for discussion of challenges and opportunities in the development of chemical control.
To further integration of European academic and industrial research communities in developing a common research framework in the utilisation of chemical control.
To Encourage younger researchers and develop new groups (e.g in Central/Eastern Europe and the Balkans.
To develop a coherent research programme that will allow methodologies for control of molecular dissociation pathways to be developed.
To integrate researchers from femtosecond chemistry, electron chemistry, and scanning tunnel microscopy and share expertise and skills.

24. EURONanochem: The programme
Hosting an annual Meeting in Europe (link to ESF EIPAM and COST ECCL)
Develop international links ( USA; Japan and Australia)
Training -workshops and schools
Industrial forums