The goal of our research activities is to bridge the knowledge gap between isolated, nanoscale particles in the gas phase and condensed matter. To this end, we develop methods to characterize the structure, reactivity and dynamics of clusters, nanoparticles and fluid interfaces using state-of-the-art mass spectrometric and laser spectroscopic techniques.

Abbildung der Wechselwirkung eines Nanopartikel mit Laserstrahlen in einer Paulfalle.
We are developing worldwide unique measurement methods for the high-precision characterization of single nanoparticles in the gas phase (Art work: Benjamin Hoffmann)

Our Research Projects

Nanoparticle samples are typically characterized by both physical and chemical heterogeneity. This leads, for example, to reduced performance in technological applications. Performance optimization requires insight into the intrinsic properties of individual nanoparticles and how they contribute to the properties of the ensemble. However, most experimental single nanoparticle methods study deposited particles whose properties are perturbed by either the carrier or neighboring particles. Characterizing only the intrinsic nanoparticle properties requires their isolation in the gas phase.

Research topics

  • Single nanoparticle mass spectrometry
  • UV/Vis- and IR-spectroscopy
  • Determination of adsorption energies
  • Elucidation of size-dependent effects in the size range from 5 to 100 nm
Abbildung der Wechselwirkung eines Nanopartikel mit Laserstrahlen in einer Paulfalle.
We are developing worldwide unique measurement methods for the high-precision characterization of single nanoparticles in the gas phase (Art work: Benjamin Hoffmann)

The properties of water and the particles dissolved in it are largely determined by the locally formed hydrogen bond network. A detailed understanding of these interactions is of interdisciplinary interest. For example, hydrogen bonds play a central role in the description of proton transfer reactions (enzymatic catalysis), the dissolution behavior of inorganic salts (solvation), the tertiary structure of biomolecules (peptide and protein folding), or the formation and properties of aerosols (nucleation) in the atmosphere, which is still not well understood at the molecular level. This is the starting point of this project, in which structural motifs are investigated by means of vibrational spectroscopy of gas phase clusters as a function of the degree of hydration and temperature under well-defined conditions. By stepwise attachment of individual water molecules, the transition from isolated to fully hydrated particle can be followed spectroscopically.

Structure of a microhydrated sulfate dianion
Sulfate dianions are known to form strong ion-water interactions and are symmetrically hydrated

Metal oxides play an increasingly important role as novel materials in a wide range of technical applications, e.g. as construction materials, as coatings, or in medical implants. The surface chemistry of these oxides is determined by their interaction with water and the ions dissolved in it. To optimize the lifetime (corrosion resistance) of such materials, a molecular understanding of the metal oxide/water interaction (oxide formation as well as oxide dissolution) is essential. Although there are already a large number of studies available on these interfaces, a fundamental understanding of this interaction at the molecular level is largely lacking. 

This project aims to characterize the structure and ultrafast dynamics of model systems containing strong hydrogen bonds. Hydrogen bonding interactions are key to understanding the structure and properties of water, biomolecules, self-assembled nanostructures, and molecular crystals. However, there is still much confusion about their electronic nature, a combination of van der Waals, electrostatic, and covalent contributions leading to a variety of hydrogen bonds with bond strengths ranging from 2 to 40 kcal/mol (a 20-fold range!). In particular, our understanding of strong, low-barrier hydrogen bonds and their central role in enzyme catalysis, biomolecular recognition, proton transfer across biomembranes, and proton transport in aqueous media is still incomplete.

 

Potential hypersurface of a strong hydrogen bond
Ground state wave function of delocalized symmetrically distributed proton in the protonated ammonia dimer

Inorganic acids (AH), their conjugate base anions (A‾), and water play critical roles in aerosol formation in the atmosphere. In the process of ion-induced nucleation, negative ions serve as more effective nucleation sites than positive ions. The most common anions in the troposphere and stratosphere include nitrate and bisulfate, as well as their microsolvated clusters. To understand the early steps of aerosol nucleation and gain insight into the microscopic structure of the bulk, we use infrared single and multiphoton dissociation spectroscopy (IRMPD) in combination with electronic structure calculations as a structural probe for size-selected (A‾)(AH)m(A'H)m'(H2O)n(H2)z clusters.

Structure and IR spectrum of the deprotonated sulfuric acid trimer
Structure and IR spectrum of the deprotonated sulfuric acid trimer

Transition metal oxides play a central role in the industrial use of heterogeneous catalysis. Interestingly, the underlying molecular reaction mechanisms are rarely known in detail. However, an understanding of these is necessary to contribute to the development of concepts for the preparation of catalysts with increased yield and selectivity. Within the framework of SFB 546 "Vanadium oxide aggregates" (1999-2011), we have built up a long-standing expertise in this respect, how spectroscopic studies of the structure, reactivity and dynamics on tailored metal oxide clusters in the gas phase can be used to investigate fundamental questions using this simple model system. This includes, for example, studies (a) on the correlation between local structure and reactivity, (b) on the identification of the spectroscopic fingerprint of active groups, (c) on the interaction between active groups and support materials, (d) on the calibration of quantum chemical computational methods, and (e) on the identification of reactive intermediates.

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Wilhelm-Ostwald-Institute

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