arXiv subjects

Michael Dürr

Publications and source records attributed to Michael Dürr.

3 recordsLinked to original sources

arXiv2020

Fast Molecular Compression by a Hyperthermal Collision Gives Bond-Selective Mechanochemistry

Using electrospray ion beam deposition, we collide the complex molecule Reichardt's Dye (C41H30NO+) at low, hyperthermal translational energy (2-50 eV) with a Cu(100) surface and image the outcome at single-molecule level by scanning tunneling microscopy. We observe bond-selective reaction induced by the translational kinetic energy. The collision impulse compresses the molecule and bends specific bonds, prompting them to react selectively. This dynamics drives the system to seek thermally inaccessible reactive pathways, since the compression timescale (sub-ps) is much shorter than the thermalization timescale (ns), thereby yielding reaction products that are unobtainable thermally.

physics.chem-ph↗

arXiv2016

Site-specific reactivity of ethylene at distorted dangling bond configurations on Si(001)

We report differences in adsorption and reaction energetics for ethylene on Si(001) with respect to different dangling bond configurations induced by hydrogen precoverage as obtained via density functional theory calculations. This can help to understand the influence of surface defects and precoverage on the reactivity of organic molecules on semiconductor surfaces in general. Our results show that the reactivity on surface dimers fully enclosed by hydrogen covered atoms is essentially unchanged compared to the clean surface. This is confirmed by our scanning tunnelling microscopy measurements. On the contrary, adsorption sites with partially covered surface dimers show a drastic increase in reactivity. This is due to a lowering of the reaction barrier by more than fifty percent compared to the clean surface, which is in line with previous experiments. Adsorption on dimers enclosed by molecule (ethylene) covered surface atoms is reported to have a highly decreased reactivity, a result of destabilization of the intermediate state due to steric repulsion, as quantified with the periodic energy decomposition analysis (pEDA). Furthermore, an approach for the calculation of Gibbs energies of adsorption based on statistical thermodynamics considerations is applied to the system. The results show that the loss in molecular entropy leads to a significant destabilization of adsorption states.

physics.chem-ph↗

arXiv2016

Chemoselective Reactivity of Bifunctional Cyclooctynes on Si(001)

Controlled organic functionalization of silicon surfaces as integral part of semiconductor technology offers new perspectives for a wide range of applications. The high reactivity of the silicon dangling bonds, however, presents a major hindrance for the first basic reaction step of such a functionalization, i.e., the chemoselective attachment of bifunctional organic molecules on the pristine silicon surface. We overcome this problem by employing cyclooctyne as the major building block of our strategy. Functionalized cyclooctynes are shown to react on Si(001) selectively via the strained cyclooctyne triple bond while leaving the side groups intact. The achieved selectivity originates from the distinctly different adsorption dynamics of the separate functionalities: A direct adsorption pathway is demonstrated for cyclooctyne as opposed to the vast majority of other organic functional groups. The latter ones react on Si(001) via a metastable intermediate which makes them effectively unreactive in competition with the direct pathway of cyclooctyne's strained triple bond.

physics.chem-ph↗