Weyl spin-momentum locking in a chiral topological semimetal.

Spin-orbit coupling in noncentrosymmetric crystals leads to spin-momentum locking - a directional relationship between an electron's spin angular momentum and its linear momentum. Isotropic orthogonal Rashba spin-momentum locking has been studied for decades, while its counterpart, isotropic parallel Weyl spin-momentum locking has remained elusive in experiments. Theory predicts that Weyl spin-momentum locking can only be realized in structurally chiral cubic crystals in the vicinity of Kramers-Weyl or multifold fermions. Here, we use spin- and angle-resolved photoemission spectroscopy to evidence Weyl spin-momentum locking of multifold fermions in the chiral topological semimetal PtGa. We find that the electron spin of the Fermi arc surface states is orthogonal to their Fermi surface contour for momenta close to the projection of the bulk multifold fermion at the Γ point, which is consistent with Weyl spin-momentum locking of the latter. The direct measurement of the bulk spin texture of the multifold fermion at the R point also displays Weyl spin-momentum locking. The discovery of Weyl spin-momentum locking may lead to energy-efficient memory devices and Josephson diodes based on chiral topological semimetals.

Sterically Selective [3 + 3] Cycloaromatization in the On-Surface Synthesis of Nanographenes.

Surface-catalyzed reactions have been used to synthesize carbon nanomaterials with atomically predefined structures. The recent discovery of a gold surface-catalyzed [3 + 3] cycloaromatization of isopropyl substituted arenes has enabled the on-surface synthesis of arylene-phenylene copolymers, where the surface activates the isopropyl substituents to form phenylene rings by intermolecular coupling. However, the resulting polymers suffered from undesired cross-linking when more than two molecules reacted at a single site. Here we show that such cross-links can be prevented through steric protection by attaching the isopropyl groups to larger arene cores. Upon thermal activation of isopropyl-substituted 8,9-dioxa-8a-borabenzo[fg]tetracene on Au(111), cycloaromatization is observed to occur exclusively between the two molecules. The cycloaromatization intermediate formed by the covalent linking of two molecules is prevented from reacting with further molecules by the wide benzotetracene core, resulting in highly selective one-to-one coupling. Our findings extend the versatility of the [3 + 3] cycloaromatization of isopropyl substituents and point toward steric protection as a powerful concept for suppressing competing reaction pathways in on-surface synthesis.

Asymmetric Molecular Adsorption and Regioselective Bond Cleavage on Chiral PdGa Crystals.

Homogenous enantioselective catalysis is nowadays the cornerstone in the manufacturing of enantiopure substances, but its technological implementation suffers from well-known impediments like the lack of endurable catalysts exhibiting long-term stability. The catalytically active intermetallic compound Palladium-Gallium (PdGa), conserving innate bulk chirality on its surfaces, represent a promising system to study asymmetric chemical reactions by heterogeneous catalysis, with prospective relevance for industrial processes. Here, this work investigates the adsorption of 10,10'-dibromo-9,9'-bianthracene (DBBA) on the PdGa:A( 1 ¯ 1 ¯ 1 ¯ $\bar{1}\bar{1}\bar{1}$ ) Pd3-terminated surface by means of scanning tunneling microscopy (STM) and spectroscopy (STS). A highly enantioselective adsorption of the molecule evolving into a near 100% enantiomeric excess below room temperature is observed. This exceptionally high enantiomeric excess is attributed to temperature activated conversion of the S to the R chiral conformer. Tip-induced bond cleavage of the R conformer shows a very high regioselectivity of the DBBA debromination. The experimental results are interpreted by density functional theory atomistic simulations. This work extends the knowledge of chirality transfer onto the enantioselective adsorption of non-planar molecules and manifests the ensemble effect of PdGa surfaces resulting in robust regioselective debromination.

Spin-Stabilization by Coulomb Blockade in a Vanadium Dimer in WSe2.

Charged dopants in 2D transition metal dichalcogenides (TMDs) have been associated with the formation of hydrogenic bound states, defect-bound trions, and gate-controlled magnetism. Charge-transfer at the TMD-substrate interface and the proximity to other charged defects can be used to regulate the occupation of the dopant's energy levels. In this study, we examine vanadium-doped WSe2 monolayers on quasi-freestanding epitaxial graphene, by high-resolution scanning probe microscopy and ab initio calculations. Vanadium atoms substitute W atoms and adopt a negative charge state through charge donation from the graphene substrate. VW-1 dopants exhibit a series of occupied p-type defect states, accompanied by an intriguing electronic fine-structure that we attribute to hydrogenic states bound to the charged impurity. We systematically studied the hybridization in V dimers with different separations. For large dimer separations, the 2e- charge state prevails, and the magnetic moment is quenched. However, the Coulomb blockade in the nearest-neighbor dimer configuration stabilizes a 1e- charge state. The nearest-neighbor V-dimer exhibits an open-shell character for the frontier defect orbital, giving rise to a paramagnetic ground state. Our findings provide microscopic insights into the charge stabilization and many-body effects of single dopants and dopant pairs in a TMD host material.

Growth Optimization and Device Integration of Narrow-Bandgap Graphene Nanoribbons.

The electronic, optical, and magnetic properties of graphene nanoribbons (GNRs) can be engineered by controlling their edge structure and width with atomic precision through bottom-up fabrication based on molecular precursors. This approach offers a unique platform for all-carbon electronic devices but requires careful optimization of the growth conditions to match structural requirements for successful device integration, with GNR length being the most critical parameter. In this work, the growth, characterization, and device integration of 5-atom wide armchair GNRs (5-AGNRs) are studied, which are expected to have an optimal bandgap as active material in switching devices. 5-AGNRs are obtained via on-surface synthesis under ultrahigh vacuum conditions from Br- and I-substituted precursors. It is shown that the use of I-substituted precursors and the optimization of the initial precursor coverage quintupled the average 5-AGNR length. This significant length increase allowed the integration of 5-AGNRs into devices and the realization of the first field-effect transistor based on narrow bandgap AGNRs that shows switching behavior at room temperature. The study highlights that the optimized growth protocols can successfully bridge between the sub-nanometer scale, where atomic precision is needed to control the electronic properties, and the scale of tens of nanometers relevant for successful device integration of GNRs.

On-surface Synthesis: What Happens Behind the Scenes?

On-surface synthesis has become a powerful approach to produce low-dimensional carbon-based nanostructures with atomistic precision. A large variety of analytical tools and methods are available to provide efficient monitoring of on-surface reactions, among which, scanning probe microscopy (SPM) has proven to be particularly efficient to characterize reaction intermediates and products down to the atomic scale. Nevertheless, due to limited temporal resolution, difficulties to explore the full temperature range, and lack of identifying the chemical environment of all elements involved in on-surface processes, SPM is ideally complemented with temperature programmed X-ray photoelectron spectroscopy (TP-XPS). In this short review, we aim to unveil some of the capabilities of synchrotron based TP-XPS reporting on our own research on Ullmann-type on-surface coupling reactions.

Asymmetric Elimination Reaction on Chiral Metal Surfaces.

The production of enantiopure materials and molecules is of uttermost relevance in research and industry in numerous contexts, ranging from nonlinear optics to asymmetric synthesis. In the context of the latter, dehalogenation, which is an essential reaction step for a broad class of chemical reactions, is investigated; specifically, dehalogenation of prochiral 5-bromo-7-methylbenz(a)anthracene (BMA) on prototypical, chiral, intermetallic PdGa{111} surfaces under ultrahigh vacuum conditions. Asymmetric halogen elimination is demonstrated by combining temperature-programmed X-ray photoelectron spectroscopy, scanning probe microscopy, and density functional theory. On the PdGa{111} surfaces, the difference in debromination temperatures for the two BMA surface enantiomers amounts up to an unprecedented 46 K. The significant dependence of the dehalogenation temperature of the BMA surface enantiomers on the atomic termination of the PdGa{111} surfaces implies that the ensemble effect is pronounced in this reaction step. These findings evidence enantiospecific control and hence promote intrinsically chiral crystals for asymmetric on-surface synthesis.

On-surface synthesis of organocopper metallacycles through activation of inner diacetylene moieties.

The design of organometallic complexes is at the heart of modern organic chemistry and catalysis. Recently, on-surface synthesis has emerged as a disruptive paradigm to design previously precluded compounds and nanomaterials. Despite these advances, the field of organometallic chemistry on surfaces is still at its infancy. Here, we introduce a protocol to activate the inner diacetylene moieties of a molecular precursor by copper surface adatoms affording the formation of unprecedented organocopper metallacycles on Cu(111). The chemical structure of the resulting complexes is characterized by scanning probe microscopy and X-ray photoelectron spectroscopy, being complemented by density functional theory calculations and scanning probe microscopy simulations. Our results pave avenues to the engineering of organometallic compounds and steer the development of polyyne chemistry on surfaces.

Asymmetric azide-alkyne Huisgen cycloaddition on chiral metal surfaces.

Achieving fundamental understanding of enantioselective heterogeneous synthesis is marred by the permanent presence of multitudinous arrangements of catalytically active sites in real catalysts. In this study, we address this issue by using structurally comparatively simple, well-defined, and chiral intermetallic PdGa{111} surfaces as catalytic substrates. We demonstrate the impact of chirality transfer and ensemble effect for the thermally activated azide-alkyne Huisgen cycloaddition between 3-(4-azidophenyl)propionic acid and 9-ethynylphenanthrene on these threefold symmetric intermetallic surfaces under ultrahigh vacuum conditions. Specifically, we encounter a dominating ensemble effect for this reaction as on the Pd3-terminated PdGa{111} surfaces no stable heterocoupled structures are created, while on the Pd1-terminated PdGa{111} surfaces, the cycloaddition proceeds regioselectively. Moreover, we observe chirality transfer from the substrate to the reaction products, as they are formed enantioselectively on the Pd1-terminated PdGa{111} surfaces. Our results evidence a determinant ensemble effect and the immense potential of PdGa as asymmetric heterogeneous catalyst.

Weyl fermions, Fermi arcs, and minority-spin carriers in ferromagnetic CoS2.

Magnetic Weyl semimetals are a newly discovered class of topological materials that may serve as a platform for exotic phenomena, such as axion insulators or the quantum anomalous Hall effect. Here, we use angle-resolved photoelectron spectroscopy and ab initio calculations to discover Weyl cones in CoS2, a ferromagnet with pyrite structure that has been long studied as a candidate for half-metallicity, which makes it an attractive material for spintronic devices. We directly observe the topological Fermi arc surface states that link the Weyl nodes, which will influence the performance of CoS2 as a spin injector by modifying its spin polarization at interfaces. In addition, we directly observe a minority-spin bulk electron pocket in the corner of the Brillouin zone, which proves that CoS2 cannot be a true half-metal.

Observation and control of maximal Chern numbers in a chiral topological semimetal.

Topological semimetals feature protected nodal band degeneracies characterized by a topological invariant known as the Chern number (C). Nodal band crossings with linear dispersion are expected to have at most [Formula: see text], which sets an upper limit to the magnitude of many topological phenomena in these materials. Here, we show that the chiral crystal palladium gallium (PdGa) displays multifold band crossings, which are connected by exactly four surface Fermi arcs, thus proving that they carry the maximal Chern number magnitude of 4. By comparing two enantiomers, we observe a reversal of their Fermi-arc velocities, which demonstrates that the handedness of chiral crystals can be used to control the sign of their Chern numbers.

Handedness-dependent quasiparticle interference in the two enantiomers of the topological chiral semimetal PdGa.

It has recently been proposed that combining chirality with topological band theory results in a totally new class of fermions. Understanding how these unconventional quasiparticles propagate and interact remains largely unexplored so far. Here, we use scanning tunneling microscopy to visualize the electronic properties of the prototypical chiral topological semimetal PdGa. We reveal chiral quantum interference patterns of opposite spiraling directions for the two PdGa enantiomers, a direct manifestation of the change of sign of their Chern number. Additionally, we demonstrate that PdGa remains topologically non-trivial over a large energy range, experimentally detecting Fermi arcs in an energy window of more than 1.6 eV that is symmetrically centered around the Fermi level. These results are a consequence of the deep connection between chirality in real and reciprocal space in this class of materials, and, thereby, establish PdGa as an ideal topological chiral semimetal.

Molecular motor crossing the frontier of classical to quantum tunneling motion.

The reliability by which molecular motor proteins convert undirected energy input into directed motion or transport has inspired the design of innumerable artificial molecular motors. We have realized and investigated an artificial molecular motor applying scanning tunneling microscopy (STM), which consists of a single acetylene (C2H2) rotor anchored to a chiral atomic cluster provided by a PdGa(111) surface that acts as a stator. By breaking spatial inversion symmetry, the stator defines the unique sense of rotation. While thermally activated motion is nondirected, inelastic electron tunneling triggers rotations, where the degree of directionality depends on the magnitude of the STM bias voltage. Below 17 K and 30-mV bias voltage, a constant rotation frequency is observed which bears the fundamental characteristics of quantum tunneling. The concomitantly high directionality, exceeding 97%, implicates the combination of quantum and nonequilibrium processes in this regime, being the hallmark of macroscopic quantum tunneling. The acetylene on PdGa(111) motor therefore pushes molecular machines to their extreme limits, not just in terms of size, but also regarding structural precision, degree of directionality, and cross-over from classical motion to quantum tunneling. This ultrasmall motor thus opens the possibility to investigate in operando effects and origins of energy dissipation during tunneling events, and, ultimately, energy harvesting at the atomic scales.

Near-Enantiopure Trimerization of 9-Ethynylphenanthrene on a Chiral Metal Surface.

Enantioselectivity in heterogeneous catalysis strongly depends on the chirality transfer between catalyst surface and all reactants, intermediates, and the product along the reaction pathway. Herein we report the first enantioselective on-surface synthesis of molecular structures from an initial racemic mixture and without the need of enantiopure modifier molecules. The reaction consists of a trimerization via an unidentified bonding motif of prochiral 9-ethynylphenanthrene (9-EP) upon annealing to 500 K on the chiral Pd3 -terminated PdGa{111} surfaces into essentially enantiopure, homochiral 9-EP propellers. The observed behavior strongly contrasts the reaction of 9-EP on the chiral Pd1 -terminated PdGa{111} surfaces, where 9-EP monomers that are in nearly enantiopure configuration, dimerize without enantiomeric excess. Our findings demonstrate strong chiral recognition and a significant ensemble effect in the PdGa system, hence highlighting the huge potential of chiral intermetallic compounds for enantioselective synthesis and underlining the importance to control the catalytically active sites at the atomic level.

On-Surface Synthesis of Cumulene-Containing Polymers via Two-Step Dehalogenative Homocoupling of Dibromomethylene-Functionalized Tribenzoazulene.

Cumulene compounds are notoriously difficult to prepare and study because their reactivity increases dramatically with the increasing number of consecutive double bonds. In this respect, the emerging field of on-surface synthesis provides exceptional opportunities because it relies on reactions on clean metal substrates under well-controlled ultrahigh-vacuum conditions. Here we report the on-surface synthesis of a polymer linked by cumulene-like bonds on a Au(111) surface via sequential thermally activated dehalogenative C-C coupling of a tribenzoazulene precursor equipped with two dibromomethylene groups. The structure and electronic properties of the resulting polymer with cumulene-like pentagon-pentagon and heptagon-heptagon connections have been investigated by means of scanning probe microscopy and spectroscopy methods and X-ray photoelectron spectroscopy, complemented by density functional theory calculations. Our results provide perspectives for the on-surface synthesis of cumulene-containing compounds, as well as protocols relevant to the stepwise fabrication of carbon-carbon bonds on surfaces.

Reversible Dehalogenation in On-Surface Aryl-Aryl Coupling.

In the emerging field of on-surface synthesis, dehalogenative aryl-aryl coupling is unarguably the most prominent tool for the fabrication of covalently bonded carbon-based nanomaterials. Despite its importance, the reaction kinetics are still poorly understood. Here we present a comprehensive temperature-programmed x-ray photoelectron spectroscopy investigation of reaction kinetics and energetics in the prototypical on-surface dehalogenative polymerization of 4,4''-dibromo-p-terphenyl into poly(para-phenylene) on two coinage metal surfaces, Cu(111) and Au(111). We find clear evidence for reversible dehalogenation on Au(111), which is inhibited on Cu(111) owing to the formation of organometallic intermediates. The incorporation of reversible dehalogenation in the reaction rate equations leads to excellent agreement with experimental data and allows extracting the relevant energy barriers. Our findings deepen the mechanistic understanding and call for its reassessment for surface-confined aryl-aryl coupling on the most frequently used metal substrates.

On-Surface Growth Dynamics of Graphene Nanoribbons: The Role of Halogen Functionalization.

On-surface synthesis is a powerful route toward the fabrication of specific graphene-like nanostructures confined in two dimensions. This strategy has been successfully applied to the growth of graphene nanoribbons of diverse width and edge morphology. Here, we investigate the mechanisms driving the growth of 9-atom wide armchair graphene nanoribbons by using scanning tunneling microscopy, fast X-ray photoelectron spectroscopy, and temperature-programmed desorption techniques. Particular attention is given to the role of halogen functionalization (Br or I) of the molecular precursors. We show that the use of iodine-containing monomers fosters the growth of longer graphene nanoribbons (average length of 45 nm) due to a larger separation of the polymerization and cyclodehydrogenation temperatures. Detailed insight into the growth process is obtained by analysis of kinetic curves extracted from the fast X-ray photoelectron spectroscopy data. Our study provides fundamental details of relevance to the production of future electronic devices and highlights the importance of not only the rational design of molecular precursors but also the most suitable reaction pathways to achieve the desired final structures.

Heteroatom-Doped Perihexacene from a Double Helicene Precursor: On-Surface Synthesis and Properties.

We report on the surface-assisted synthesis and spectroscopic characterization of the hitherto longest periacene analogue with oxygen-boron-oxygen (OBO) segments along the zigzag edges, that is, a heteroatom-doped perihexacene 1. Surface-catalyzed cyclodehydrogenation successfully transformed the double helicene precursor 2, i.e., 12a,26a-dibora-12,13,26,27-tetraoxa-benzo[1,2,3-hi:4,5,6-h'i']dihexacene, into the planar perihexacene analogue 1, which was visualized by scanning tunneling microscopy and noncontact atomic force microscopy. X-ray photoelectron spectroscopy, Raman spectroscopy, together with theoretical modeling, on both precursor 2 and product 1, provided further insights into the cyclodehydrogenation process. Moreover, the nonplanar precursor 2 underwent a conformational change upon adsorption on surfaces, and one-dimensional self-assembled superstructures were observed for both 2 and 1 due to the presence of OBO units along the zigzag edges.