Methods for accurately computing the interaction of molecules with metal surfaces are critical to understanding and thereby improving heterogeneous catalysis.

This perspective addresses four challenges facing theorists whose aim is to make quantitatively accurate predictions for reactions of molecules on metal surfaces, and suggests ways of meeting these challenges, focusing on dissociative chemisorption reactions of H2, N2, and CH4.

Catalysis is of extreme relevance in the production of everyday materials and plays a central role in many aspects of our life.

This thesis describes the use of a combined approach of computational and experimental techniques to gain novel insights to understand the glycosylation reaction and its reactive intermediates.

Promotor: A. Doelman, Co-promotor: J.D.M. Rademacher

In this thesis we have discussed several parameters that affect the electrochemical conversion of enviromentaly harmful molecules such as nitrates and carbon dioxide to more valuable and less deleterious compounds, in order to cast light onto the mechanism of the reaction to achieve an efficient and…

Heterogeneous catalysis is essential to many industrial applications. These catalysts are often comprised of supported nanoparticles, which contain various different surface sites.

How can we make the production of chlorine cheaper and more friendly for the environment?

Promotor: Prof.dr. G.J. Kroes

Koper

Promotor: Prof.dr. T.J. Aartsma, Co-promotor: R.N. Frese

This thesis has shed light on some of the ways in which the local electrolyte composition can differ from the bulk and how these changes in the local reaction environment can determine the activity and/or selectivity of two important electrocatalytic reactions, namely, electrochemical CO2 reduction…

It is a common technique in global optimization with expensive black-box functions to learn a surrogate-model of the response function from past evaluations and use it to decide on the location of future evaluations.

The glycosylation reaction is a pivotal reaction in creating new and complex oligosaccharides.

In this dissertation, the synthesis and characterization of a series of iron complexes based on different ligand platforms are described.

Promotor: Prof.dr. E. Bouwman

Historiography of science is in its current self-image a non-evaluative discipline. Its main goal is to understand past processes of knowledge formation on their own terms. In the last few decades this approach has greatly improved our understanding of the phenomenon of science. Yet, something strange…

Microneedle-based vaccination has several advantages over vaccination by using conventional hypodermic needles.

Promotor: M.T.M. Koper, Co-Promotor: L.B.F. Juurlink

Metals surfaces form a group of effective catalysts for the reaction of small molecules such as hydrogen (H2).

The research presented in this thesis makes use of small molecules (as H2 , D2 and O2 ) on well-defined single crystal surfaces (flat Pt(111), flat Cu(211) and curved Pt(111)) to elucidate the role of surface structure and degrees of freedom in the reactant in specific surface reactions.

A difficulty of studies on chemical kinetics are the reaction time scales and detection of their intermediates.

Hetterscheid

Although it is often assumed that the stereochemistry in Ugi multicomponent reactions is determined in the final Mumm rearrangement step, experimental and computational evidence that Ugi reactions on hydroxylated pyrrolines proceed under kinetic control is reported.

Promotores: G.W. Canters, T.J. Aartsma

Promotor: Arjen Doelman, Co-promotor: Vivi Rottschäfer

Promotor: E. Bouwman, Co-promotor: S. Bonnet

The local ordering of atoms at the surface of a metallic particle determines its catalytic activity and selectivity. As energy systems of the future will be based on efficient catalytic conversion of small molecules in closed cycles, we study how structural effects of catalysts can be used to our ad…

The dissociative chemisorption of a molecule on a transition metal surface represents a rate-limiting step in many heterogeneously catalyzed processes, whereby most chemicals are made. In spite of the importance of this reaction, an accurate first principles approach to modeling it does not yet exist.…

In this thesis chemical and physical processes in the ice mantles on interstellar dust grains are studied.

Organizations often announce their protest activities prior to their implementation to mobilize awareness, recruit supporters, and receive media attention. We are interested in the effectiveness of protest announcements—that is, under what conditions governments make concessions to avoid having an announced…

Human civilization consumes a huge amount of fossil fuels, which has resulted in an atmospheric CO2 level which has not been higher in over 800 millennia.

We review the state-of-the-art in the theory of dissociative chemisorption (DC) of small gas phase molecules on metal surfaces, which is important to modeling heterogeneous catalysis for practical reasons, and for achieving an understanding of the wealth of experimental information that exists for this…

Several techniques are explored for going beyond the born-oppenheimer static surface model for molecule-surface reactions.

A semi-empirical version of the specific reaction parameter approach to density functional theory (SRP-DFT) has been remarkably successful at predicting dissociative chemisorption probability vs. incidence energy curves for reactions on metal surfaces. New quantum Monte Carlo (QMC) calculations on the…

Promotor: M.T.M. Koper, Co-Promotor: L.B.F. Juurlink

Promotor: Prof.dr. H.V.J. Linnartz, Co-Promotores: S. Ioppolo, H.M. Cuppen

Density functional theory (DFT) with so-called semi-local exchange has been remarkable accurate for some dissociative chemisorption reactions on metals, but it has notoriously failed for others. A team of researchers from the University of California at Irvine and the Leiden Institute of Chemistry have…

In this dissertation iron-based homogeneous catalysts were synthesized, characterized and investigated for water oxidation activity.

Poly(lactic-co-glycolic acid) (PLGA) particles have been extensively studied as biodegradable delivery system to improve the potency and safety of protein-based vaccines. In this study we analyzed how the size of PLGA particles, and hence their ability to be engulfed by dendritic cells (DC), affects…

This thesis systematically studies the physicochemical properties of non-planar, propeller-shaped, polycyclic aromatic hydrocarbons. The synthesis of several so-called propellerenes is described on a gram scale, using optimized procedures aimed at using less hazardous reagents and reducing the amount…

The dissociative chemisorption of methane on metal surfaces is of fundamental and practical interest, being a rate-limiting step in the steam reforming process. The reaction is best modeled with quantum dynamics calculations, but these are currently not guaranteed to produce accurate results because…

Ineke Smit defended her thesis on 17 September 2019

Promotor: M.T.M. Koper, Co-Promotor: F. Calle-Vallejo

Fundamental understanding of molecular reactions on metal surfaces is important for improving heterogeneous catalysis.

Promotores: Arjen Doelman, Jens Rademacher, Max Rietkerk

An accurate description of reactive scattering of molecules on metal surfaces often requires the modeling of energy transfer between the molecule and the surface phonons. Although ab initio molecular dynamics (AIMD) can describe this energy transfer, AIMD is at present untractable for reactions with…

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