arXiv subjects

E. Charles H. Sykes

Publications and source records attributed to E. Charles H. Sykes.

5 recordsLinked to original sources

arXiv2026

An Atlas and Design Rules for Single- and Dual-Atom Alloys

A long-standing goal across heterogeneous catalysis, materials science, and condensed matter physics is to design alloys with prescribed local atomic arrangements. Recent experiments show that dilute trimetallic alloys unlock chemistries inaccessible to bimetallics, but realizing this potential requires knowing which dopant structures form across an enormous compositional space. Using density functional theory screening, we construct an atlas spanning transition metal single- and dual-atom alloys in Cu and Ag surfaces, which we validate by scanning tunneling microscopy. The stability follows an electron count: dopants pair most strongly when their combined d-electron count approaches ten. Host metal and surface facet can be used to tune the resulting active site motifs, while size mismatch and spin explain variations around this trend. We further introduce a reactor-anchor concept, in which one dopant anchors a second, otherwise bulk-segregating dopant at the surface. Together, these results establish design principles for engineering alloys with targeted active site structures.

cond-mat.mtrl-sci↗

arXiv2021

Periodic Trends in Adsorption Energies Around Single-Atom Alloy Active Sites

Single-Atom Alloys (SAAs) are a special class of alloy surface catalysts that offer well defined, isolated active sites in a more inert metal host. The dopant sites are generally assumed to have little or no influence on the properties of the host metal, and transport of chemical reactants and products to and from the dopant sites is generally assumed to be facile. Here, by performing density functional theory calculations and surface science experiments, we identify a new physical effect on SAA surfaces, whereby adsorption is destabilised by up to 300 meV on host sites within the perimeter of the reactive dopant site. We identify periodic trends for this behaviour, and demonstrate a zone of exclusion around the reactive sites for a range of adsorbates and combinations of host and dopant metals. Experiments confirm an increased barrier for CO diffusion towards the dopant on a RhCu SAA. This effect offers new possibilities for understanding and designing active sites with tunable energetic landscapes surrounding them.

cond-mat.mtrl-sci↗

arXiv2020

An low-cost spectrum analyzer for trouble shooting noise sources in scanning probe microscopy

Scanning probe microscopes are notoriously sensitive to many types of external and internal interference including electrical, mechanical and acoustic noise. Sometimes noise can even be misinterpreted as real features in the images. Therefore, quantification of the frequency and magnitude of any noise is key to discovering the source and eliminating it from the system. While commercial spectrum analyzers are perfect for this task, they are rather expensive and not always available. We present a simple, cost effective solution in the form of an audio output from the instrument coupled to a smart phone spectrum analyzer application. Specifically, the scanning probe signal, e.g. the tunneling current of a scanning tunneling microscope is fed to the spectrum analyzer which Fourier transforms the time domain acoustic signal into the frequency domain. When the scanning probe is in contact with the sample, but not scanning, the output is a spectrum containing both the amplitude and frequency of any periodic noise affecting the microscope itself, enabling troubleshooting to begin.

physics.app-ph↗

arXiv2018

Chirality at two-dimensional surfaces: A perspective from small molecule alcohol assembly on Au(111)

The delicate balance between H-bonding and van der Waals interactions determine the stability,structure and chirality of many molecular and supramolecular aggregates weakly adsorbed on solid surfaces.Yet the inherent complexity of these systems makes their experimental study at the molecular level very challenging.Small alcohols adsorbed on metal surfaces have become a useful model system to gain fundamental insight into the interplay of such molecule-surface and molecule-molecule interactions.Here, through a combination of scanning tunneling microscopy and density functional theory,we compare and contrast the adsorption and self-assembly of a range of small alcohols from methanol to butanol on Au(111).We find that that longer chained alcohols prefer to form zigzag chains held together by extended H-bonded networks between adjacent molecules.When alcohols bind to a metal surface datively via one of the two lone electron pairs of the oxygen atom they become chiral.Therefore,the chain structures are formed by a H-bonded network between adjacent molecules with alternating adsorbed chirality.These chain structures accommodate longer alkyl tails through larger unit cells, while the position of the hydroxyl group within the alcohol molecule can produce denser unit cells that maximize intermolecular interactions.Interestingly,when intrinsic chirality is introduced into the molecule as in the case of 2-butanol the assembly changes completely and square packing structures with chiral pockets are observed. This is rationalized by the fact that the intrinsic chirality of the molecule directs the chirality of the adsorbed hydroxyl group meaning that heterochiral chain structures cannot form.Overall this study provides a general framework for understanding the effect of simple alcohol molecular adstructures on H-bonded aggregates and paves the way for rationalizing 2D chiral supramolecular assembly.

cond-mat.mtrl-sci↗

arXiv2016

The Interplay of Covalency, Hydrogen Bonding and Dispersion Leads to a Long Range Chiral Network: The Example of 2-Butanol

The assembly of complex structures is driven by an interplay between several intermolecular interactions, from strong covalent bonds to weaker dispersion forces. Surface-based self-assembly is particularly amenable to modeling and measuring these interactions in well-defined systems. This study focuses on 2-butanol, the simplest aliphatic chiral alcohol. 2-butanol shows interesting properties as a chiral modifier of surface chemistry, however, its mode of action is not fully understood. In order to probe its surface properties we employed high-resolution scanning tunneling microscopy and DFT simulations. We found a surprisingly rich degree of enantiospecific adsorption, association, chiral cluster growth and ultimately long range, highly ordered chiral templating. Firstly, the chiral molecules acquire a second chiral center when adsorbed to the surface via dative bonding of one of the oxygen atom lone pairs. This interaction is controlled via the molecule's intrinsic chiral center leading to monomers of like chirality, at both chiral centers, adsorbed on the surface. The monomers then associate into tetramers via a cyclical network of hydrogen bonds with an opposite chirality at the oxygen atom. The evolution of these square units is surprising given that the underlying surface has a hexagonal symmetry. Our DFT calculations reveal that the tetramers are able to associate with each other by weaker van der Waals interactions and tessellate in an extended square network. Our data reveals that the chirality of a simple alcohol can be transferred to its surface binding geometry, drive the directionality of hydrogen bonds and ultimately extended structure. Furthermore, this study provides the first microscopic insight into the surface properties of this important chiral modifier and provides a well-defined system for studying the network's enantioselective interaction with other molecules.

cond-mat.mtrl-sci↗