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Physical Chemistry and Nanotechnology of Interfaces

Working Group Prof. Kautek

  • In-situ-fs-microscopy in an aperture-free nearfield scaaning proobe microsope (a-SNOM)
  • In-situ-fs-Laser nanostructuring in a-SNOM
  • fs-Laser excitation of  self-organization of biological, organic and inorganic solid state surfaces in the nano-scale
  • Femto-Electrochemistry with hot electrons (picosecond current pulse electrochemistry)
  • fs-Laser-Nanostructuring
  • Bioelectrochemistry: proteins, self-organization
  • Laser cleaning of artifacts (paper, parchment, textiles, polymers)
  • fs-Laser-Medicine: Ophthalmology    

Comparison between amplified laser system (CPA) and high energy oscillators concerning repetition rate and output energy.

The activity of “Physical Chemistry and Nanotechnology of Interfaces" relies on pioneering work for more than 15 years in demonstrating femtosecond machining down to the nanscale of a broad variety of materials soon after fs-laser got available in the early nineties. Experience exists in top-down femtosecond laser ablation allowing micro- and nanomachining of 1D, 2D, and 3D structures in metals, transparent solids and biological tissues that cannot be made any other way. A special advantage is the unique possibility of congruent machining of highly inhomogeneous composite materials. Pulse durations (less than 80) provide the unique possibility to deterministically excite the electronic system by multi photon excitation resulting in unique precision in contrast to "conventional" fs-laser applications (>100 fs) where stochastic avalanche processes result in poor ablation qualities.

A novel optical setup coupling sub-60 fs-pulses into a high precision microscope will allow ultrahigh-precision processing. fs-pulses are necessary to avoid large heat affected zones (> 1µm) common with conventional ns-pulse lasers. Such non-linear phenomena can be exploited to reach supercritical intensities only in the focus of transparent bulk materials enabling laser direct-writing of 3D devices containing optical and microfluidic networks. This new approach to set up nano and microstructures can be applied to almost any transparent composite and functional material.

It was recently demonstrated that fs-laser-induced self assembly of nanostructures on solids opens a new approach to nano-structure surfaces bottom-up 
Fs-Laser ablation of solids in liquid contact can be a process for synthesizing nanoparticles and nanotubes/nanorods Thus uniformly small particles precipitate in solution. Fs-Pulsed laser deposition can serve to transfer delicate polymeric and biopolymeric materials to any substrate (fs-Laser Induced Forward Transfer, fs-LIFT) as a microprinting process avoiding thermal damage in sharp contrast to conventional nanosecond technology in LIFT.
Electrochemical scanning force microscopy allows to investigate the molecular structure of double layers and nanomanipulate electrified interfaces.
Biolectrochemistry could be demonstrated on crystalline single layer proteins on electrodes in a longterm collaboration with the Vienna University of Natural Resources and Applied Life Sciences (BOKU)

Computational Physical Chemistry and Polymere Chemistry

Working Group Prof. Podloucky, Prof. Herzig

Simulation of (Polymer) Systems

Model calculations are powerful mediators between experimental investigations and the development of theories providing a better understanding of systems on a molecular scale. Furthermore, in many cases the outcome of numerical calculations even exceeds the spectrum and resolution of experimental investigations thus allowing to check existing theories in detail and to give guidelines for new theories. Therefore, simulation methods developed into a further main pillar of science in addition to the two classical methods.

Atomistic Molecular Dynamics Simulations

For quantum mechanical calculations from first principles approximations are minimal but enormously exhaustive for a larger number of atoms restricting these methods to rather small systems only. Larger systems of size (5-10 nm)3 over a time interval of several nanoseconds may be simulated by use of classical molecular dynamics based on proper force fields describing the interactions between atoms. Properties of oligomers (small polymers) in bulk and at surfaces, e.g., may be investigated in this way.

For these types of investigations we are using the commercial software package Materials Studio (MS Modeling) from Accelrys Inc. using the Visualizer module for generating the molecules and for visualization of results, the Amorphous Cell tool for preparing periodic systems and Discover with force field COMPASS (a class-II force field optimized for the simulation of condensed phases) as the molecular dynamics engine. Relevant data not directly supported by the client are extracted from the trajectories by use of proper BTCL-scripts.

Among other projects our atomistic simulations (marked blue in the list of references) comprise the investigation of properties of (small) polymers in bulk, the interaction and orientation of molecules (e.g. silanes, dyes like eosin Y,...) adsorbed at surfaces (ZnO, TiO2) and the simulation of glass transition temperatures (polymer matrices with varying plasticizer content, amorphous carbohydrates, amorphous ice).

The picture shows a simulation box containing 456 hexane molecules (depicted as sticks) and one polyethylene chain (C120) with black (white) spheres representing carbon (hydrogen). Visualization by use of MS-Visualizer.

Mesoscale Simulations

Especially for polymer systems length scales of structural properties as well as time scales of dynamic properties are spread over several orders of magnitude. Combining groups of monomers to single segments (coarse grained chains) and applying more simple potentials characterizing the principle behavior of interactions between chain segments only make these systems accessible to simulations which are still able to yield a lot of useful results. E.g., the chain length (i.e. the number of segments of the model chain) still serves as an independent parameter which allows the calculation of a wide range of universal features depending on this parameter.

Monte Carlo simulation techniques are preferred at least as long as static properties are of interest only. They explore the phase space in an extremely efficient stochastic way (generally using "unphysical" movements which are allowed in this context) thus yielding ensemble averages from a (large) number of randomly taken snapshots of the system. Dissipative particle dynamics (DPD) is a further most promising simulation technique for mesoscale simulations; interaction parameters are closely connected to Flory Huggins parameters: therefore, the transformation of experimentally obtained parameters characteristic for specific polymers into simulation parameters as well as the back-transformation of the simulation results into the atomistic picture should be possible. Furthermore, dynamic properties are accessible as well.

For these types of investigations (marked purple in the list of references) all programs are developed and written by ourselves; among other projects our mesoscale simulations comprise the investigation of properties of linear, star-branched and ring shaped polymers in solution and bulk (size, shape, distribution of and correlation between them,…), the investigation of polymer surfaces and interfaces, polymer/polymer interactions within contact pairs as a function of separation (yielding the intermolecular excluded volume, pair distribution functions, and related quantities like concentrations dependences of characteristic data in the limit of high dilution and shielding factors for polymer/polymer reactions,…). Homopolymers as well as copolymers are examined.

The picture shows two snapshots of simulation boxes with polymers of equal length attached to the wall (periodic boundaries in other directions); concentration of chains in the right box is twice the concentration in the left one resulting in more expanded chains. Visualization by use of POVRAY.

The project "P20124: Properties of star-branched (co)-polymers" belonging to this type of investigations is funded from the Austian Science Fund (FWF) which is gratefully acknowledged.

Kinetics of Polymerization Processes

Numerical and analytical modeling yielded a sound theoretical basis for the pulsed laser polymerization (PLP) method (invented 1987 by O.F. Olaj et al.) which in the meantime is used all over the world and is an IUPAC recommended benchmark method for the determination of kinetic constants; the propagation rate constant - strictly speaking coefficient, see below - is directly available from the position of "extra-peaks" appearing in the chain length distribution of polymers prepared by pulsed-laser initiated radical polymerization. Furthermore, the method could be extended to rotating sector initiation as well as (at least in principle) to arbitrary initiation profiles and the influence of side reactions has been studied in detail.

An important feature obtained in the course of the evaluation of pair-distribution functions mentioned above was the calculation of the thermodynamic shielding factor of polymer-polymer reactions which turned out to be chain-length dependent. As a consequence, the termination rate coefficient in free radical polymerization should be chain-length dependent, too. Based on the results of the simulation, the influence of a chain-length dependence of the termination rate coefficient on kinetic data was evaluated in detail for stationary as well as for pseudostationary polymerization processes.

On the basis of experimental results corroborated by simulations in 2000 we were the first to put forward the idea that chain-length dependence is not only to be expected for the termination rate coefficient but also for the propagation rate constant, a highly interesting task with enormous consequences for the whole field of polymerization kinetics.

In recent times a lot of effort has been put into further improving the quality of kinetic data obtained by the PLP method by developing correction functions in order to consider the effect of axial dispersion inherent in the size exclusion chromatography used to obtain the distribution curves.

Furthermore, the concept of shielding parameters was extended to Z-RAFT polymerization processes. Among other things our calculations reveal that shielding is smaller and chain-length dependence is less pronounced under bad solvent conditions as compared to the situation in a good solvent. Actually, experimental results are in full accordance with this theoretical predictions.

Investigations summarized in this paragraph can be either treated by analytical methods or (especially in case of chain length dependent rate coefficients) by use of numeric methods. All programs needed are developed and written by ourselves; occasionally, the commercial software PREDICI © is used.

As an example, the figure shows the calculated influence of chain transfer on weight distributions obtained by PLP, the concentration of the transfer agent increasing from the brown curve over the red, the dark blue, and the blue to the green one.

Ab-initio

We try to understand materials properties from fundamental principles. Approaches applying such a philosophy are called first-principles or ab-initio methods.

Density functional theory

The background of all our work is the solution of Schrödinger's equation (or Dirac's equation for relativistic cases) to describe the interactions of atoms in a solid modelled by two- or threedimensionally periodic arrangements of atoms. In principal, no empirical parameters are needed for our calculations. The only - and crucial - approximation has to be made for the many body interaction of the electrons surrounding the atomic nuclei which is done in the framework of Density Functional Theory. Because of the fundamental approach our calculations require substantial computational costs depending on the size of the systems, i.e. the number of atoms in the unit cell. Systems of 50-100 atoms can still be reasonably treated on the fastest machines including workstations. Therefore we constantly work on optimization of codes and methods, and on providing sufficient access to the most powerful computer systems available. On the other hand, a first-principles approach allows the treatment of all types of atoms and many different systems with the same machinery. Therefore, the spectrum of systems which are studied is huge, ranging from free atoms, clusters, bulk solids, interfaces, surfaces and molecules on surfaces. For such systems important physical and chemical properties can be derived solely based on hard numbers without any empirical parameters.

Surfaces & Bulk, Alloys & Compounds

It is worthwhile to have a look at the general activities of the Scientific Computing Community of the University of Vienna. Specific contributions of our group for the years 2002: MATERIALS SCIENCE: From Schrödinger's equation to materials properties of Solid Matter, and for the year 2003: MATERIALS SCIENCE: (1) Adsorption study on a Zn Surface and (2) Density Functional Studies of Alloys and Compounds can be found there. We are also part of a joint research project in which the leading Austrian research groups in the field of surface science at the Universities of Graz, Linz, Vienna, Innsbruck and at the Technical Universites of Graz and Vienna collaborate: nsos

Intermetallics

Intermetallics are also of interest for us, because they produce so nice colors. There is a nice article by Thomas Kramar (in German).

Silicides

One of Elio's favourite subjects was the study of Silicides. Although they cannot be used for Pasta (or maybe we didn't realize) they have a lot of interesting features.

 

 

Institut für Physikalische Chemie
Universität Wien

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