Au Surface Research Articles

A Linearized Semiclassical Dynamics Study of the Multiquantum Vibrational Relaxation of NO Scattering from a Au(111) Surface.

The vibrational relaxation of NO molecules scattering from a Au(111) surface has served as the focus of efforts to understand nonadiabatic energy transfer at metal-molecule interfaces. Experimental measurements and previous theoretical efforts suggest that multiquantal NO vibrational energy relaxation occurs via electron-hole pair excitations in the metal. Here, using a linearized semiclassical approach, we accurately predict the vibrational relaxation of NO from the νi = 3 state for different incident translational energies. We also accurately capture the central role of transient electron transfer from the metal to the molecule in mediating the vibrational relaxation process but fall short of quantitatively predicting the full extent of multiquantum relaxation for high incident vibrational excitations (νi = 16).

Surface-Plasmon-Resonance Amplification of FMD Detection through Dendrimer Conjugation.

The amplification of the surface plasmon resonance (SPR) sensitivity for the foot-and-mouth disease (FMD) detection was studied using Poly(amidoamine) (PAMAM) succinamic-acid dendrimers. The dendrimers were conjugated with the complementary annealed with the aptamers capable of binding specifically to FMD peptides. The tethered layer of the dendrimer-conjugated double-stranded(ds)-aptamers was formed on the SPR sensor Au surface via a thiol bond between the aptamers and Au. After the tethered layer was formed, the surface was taken out of the SPR equipment. Then, the ds-aptamers on the surface were denatured to collect the dendrimer-conjugated single-stranded(ss)-complementary. The surface with only the remaining ss-aptamers was transferred again to the equipment. Two types of the injections, the FMD peptide only and the dendrimer-conjugated ss-complementary followed by the FMD peptides, were performed on the surface. The sensitivity was increased 20 times with the conjugation of the dendrimers, but the binding rate of the peptides became more than two times slower.

Dramatic Acceleration of the Hopf Cyclization on Gold(111): From Enediynes to Peri-Fused Diindenochrysene Graphene Nanoribbons.

Hopf et al. reported the high-temperature 6π-electrocyclization of cis-hexa-1,3-diene-5-yne to benzene in 1969. Subsequent studies using this cyclization have been limited by its very high reaction barrier. Here, we show that the reaction barrier for two model systems, (E)-1,3,4,6-tetraphenyl-3-hexene-1,5-diyne (1a) and (E)-3,4-bis(4-iodophenyl)-1,6-diphenyl-3-hexene-1,5-diyne (1b), is decreased by nearly half on a Au(111) surface. We have used scanning tunneling microscopy (STM) and noncontact atomic force microscopy (nc-AFM) to monitor the Hopf cyclization of enediynes 1a,b on Au(111). Enediyne 1a undergoes two sequential, quantitative Hopf cyclizations, first to naphthalene derivative 2, and finally to chrysene 3. Density functional theory (DFT) calculations reveal that a gold atom from the Au(111) surface is involved in all steps of this reaction and that it is crucial to lowering the reaction barrier. Our findings have important implications for the synthesis of novel graphene nanoribbons. Ullmann-like coupling of enediyne 1b at 20 °C on Au(111), followed by a series of Hopf cyclizations and aromatization reactions at higher temperatures, produces nanoribbons 12 and 13. These results show for the first time that graphene nanoribbons can be synthesized on a Au(111) surface using the Hopf cyclization mechanism.

Urease-Powered Black TiO2 Micromotors for Photothermal Therapy of Bladder Cancer.

Urease-powered nano/micromotors can move at physiological urea concentrations, making them useful for biomedical applications, such as treating bladder cancer. However, their movement in biological environments is still challenging. Herein, Janus micromotors based on black TiO2 with urease asymmetric catalytic coating were designed to take benefit of the optical properties of black TiO2 under near-infrared light and the movement capability in simulated bladder environments (urea). The black TiO2 microspheres were half-coated with a thin layer of Au, and l-Cysteine was utilized to attach the urease enzyme to the Au surface using its thiol group. Biocatalytic hydrolysis of urea through urease at biologically relevant concentrations provided the driving force for micromotors. A variety of parameters, such as urea fuel concentration, viscosity, and ionic character of the environment, were used to investigate how micromotors moved in different concentrations of urea in water, PBS, NaCl, and urine. The results indicate that micromotors are propelled through ionic self-diffusiophoresis caused by urea enzymatic catalysis. Due to their low toxicity and in vitro anticancer effect, micromotors are effective agents for photothermal therapy, which can help kill bladder cancer cells. These promising results suggest that biocompatible micromotors hold great potential for improving cancer treatment and facilitating diagnosis.

Synthesis of Tridecacene by Multistep Single-Molecule Manipulation.

Acenes represent a unique class of polycyclic aromatic hydrocarbons that have fascinated chemists and physicists due to their exceptional potential for use in organic electronics. While recent advances in on-surface synthesis have resulted in higher acenes up to dodecacene, a comprehensive understanding of their fundamental properties necessitates their expansion toward even longer homologues. Here, we demonstrate the on-surface synthesis of tridecacene via atom-manipulation-induced conformational preparation and dissociation of a trietheno-bridged precursor on a Au(111) surface. The generated tridecacene has been investigated by scanning tunneling microscopy and spectroscopy (STM/STS), combined with first-principles calculations. We observe that the STS transport gap (1.09 eV) shrinks again following the gap reopening of dodecacene (1.4 eV). Spin-polarized density functional theory calculations confirm an antiferromagnetic open-shell ground-state electronic configuration for tridecacene in the gas phase. Interestingly, tridecacene's open-shell character is significantly reduced upon interaction with the Au(111) surface despite being only physisorbed. The interaction with the surface leads to a lowering of the magnetization of tridecacene, a reduced gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), compared to the gas phase, and a reduced relative energy to the nonmagnetic state, making it nearly isoenergetic. These observations show qualitatively that the influence of the Au(111) substrate on the properties of long acenes is significant, which is important for interpreting the measured STS transport gaps. Our work contributes to a fundamental understanding of the electronic properties of long acenes, confirming a nonmonotonous length-dependent HOMO-LUMO gap, and to the development of multistep tip-assisted synthesis of elusive compounds.

Solvent-Mediated Modulation of the Au-S Bond in Dithiol Molecular Junctions.

Gold-dithiol molecular junctions have been studied both experimentally and theoretically. However, the nature of the gold-thiolate bond as it relates to the solvent has seldom been investigated. It is known that solvents can impact the electronic structure of single-molecule junctions, but the correlation between the solvent and dithiol-linked single-molecule junction conductance is not well understood. We study molecular junctions formed with thiol-terminated phenylenes from both 1-chloronaphthalene and 1-bromonaphthalene solutions. We find that the most probable conductance and the distribution of conductances are both affected by the solvent. First-principles calculations show that junction conductance depends on the binding configurations (adatom, atop, and bridge) of the thiolate on the Au surface, as has been shown previously. More importantly, we find that brominated solvents can restrict the binding of thiols to specific Au sites. This mechanism offers new insight into the effects of the solvent environment on covalent bonding in molecular junctions.

Six-dimensional quantum dynamics study for the dissociative chemisorption of H2 on pure and alloyed AgAu surfaces.

The 6D time-dependent wave packet calculations were performed to explore H2 dissociation on Ag, Au, and two AgAu alloy surfaces, using four newly fitted potential energy surfaces based on the neural network fitting to density functional theory energy points. The ligand effect resulting from the Ag-Au interaction causes a reduction in the barrier height for H2+Ag/Au(111) compared to H2+Ag(111). However, the scenario is reversed for H2+Au/Ag(111) and H2+Au(111). The 6D dissociation probabilities of H2 on Ag/Au(111) surfaces are significantly higher than those on the pure Ag(111) surface, but the corresponding results for H2 on Au/Ag(111) surfaces are substantially lower than those on the pure Au(111) surface. The reactivity of H2 on Au(111) is larger than that on Ag(111), despite Ag(111) having a slightly lower static barrier height. This can be attributed to the exceptionally small dissociation probabilities at the hcp and fcc regions, which are at least 100 times smaller compared to those at the bridge or top site for H2+Ag(111). Due to the late barrier being more pronounced, the vibrational excitation of H2 on Ag(111) is more effective in promoting the reaction than on Au(111). Moreover, a high degree of alignment dependence is detected for the four reactions, where the H2 dissociation has the highest probability at the helicopter alignment, as opposed to the cartwheel alignment.

Inelastic scattering of formaldehyde on Au(111) surface.

Inelastic scattering between gas molecules and surfaces is a fundamental process that has been investigated extensively. In recent gas-surface scattering experiments [Phys. Chem. Chem. Phys. 19, 19904 (2017)] on formaldehyde scattering off the gold surface, the scattered formaldehyde molecules had a high propensity to excite twirling motion about the C-O bond. In the work presented here, we used classical dynamics simulations to understand energy transfer in formaldehyde-surface collisions and to probe the mechanism of interconversion of translational energy to rotational energy. The simulations reveal an increase in the rotational energy distribution with an increase in collision energies and a preferential rotational excitation about the C-O bond consistent with the experiments. The high propensity to excite the twirling motion was found to arise from a steering motion about the C-O bond during the scattering process governed by the minimum energy path.

Differential local ordering of mixed crowders determines effective size and stability of ss-DNA capped gold nanoparticle.

Understanding the influence of a crowded intracellular environment on the structure and solvation of DNA functionalized gold nanoparticles (ss-DNA AuNP) is necessary for designing applications in nanomedicine. In this study, the effect of single (Gly, Ser, Lys) and mixture of amino acids (Gly+Ser, Gly+Lys, Ser+Lys) at crowded concentrations is examined on the structure of the ss-DNA AuNP using molecular dynamics simulations. Using the structural estimators such as pair correlation functions and ligand shell positional fluctuations, the solvation entropy is estimated. Combining the AuNP-solvent interaction energy with the solvation entropy estimates, the free energy of solvation of the AuNP in crowded solutions is computed. The solvation entropy favours the solvation free energy which becomes more favourable for larger effective size of AuNP in crowded solutions relative to that in water. The effective size of AuNP depends on the different propensity of the crowders to adsorb on Au surface, with the smallest crowder (Gly) having the highest propensity inducing the least effective AuNP size as compared to other single crowder solutions. In mixed crowded solutions of amino acids of variable size and chemistry, distinctive local adsorption of the crowders on the gold surface is observed that controls the additive or non-additive crowding effects which govern an increase (in Gly+Ser) or decrease (in Gly+Lys) in nanoparticle effective size respectively. The results shed light into the fundamental understanding of the influence of intracellular crowding on structure of ss-DNA AuNP and plausible employability of crowding as a tool to design programmable self-assembly of functionalized nanoparticles.

Solid-state electrochemical oxidation with polyelectrolyte membrane stamps for micro-/nanoscale pattern formation on Au surfaces.

Nanoscale-patterned Au surfaces are promising for a wide range of applications from bio/chemical sensors to high-performance electrodes. However, pattern formation using conventional resist-based methods is complex, expensive, and environmentally unfriendly. Herein, we report a novel approach for pattern formation on Au surfaces using solid-state electrochemical treatment with polymer electrolyte membrane (PEM) stamps. During electrolysis, the patterned structure of the PEM stamp was transferred onto the Au surface to form micro- and nanoscale oxide patterns. X-ray analysis of the treated surface confirmed the formation of an oxide film on the Au surface, which was subsequently reduced to metallic Au after air exposure for several weeks. Although the pattern height decreased with air exposure, a patterned structure with a height of several hundred nanometers was maintained following oxide reduction. Reflectance spectroscopy revealed that the patterned Au surface exhibited sharp reflectance peaks, the intensities and positions of which strongly depended on the measurement angle, which are key characteristics of diffraction gratings. This fast and facile electrochemical treatment process is promising for the preparation of patterned Au surfaces that can be applied in optical gratings and localized surface plasmon resonance sensors.

Hierarchical self-assembly of Au-nanoparticles into filaments: evolution and break.

We compare the assembly of individual Au nanoparticles in a vacuum and between two Au(111) surfaces via classical molecular dynamics on a timescale of 100 ns. In a vacuum, the assembly of three nanoparticles used as seeds, initially showing decahedral, truncated octahedral and icosahedral shapes with a diameter of 1.5-1.7 nm, evolves into a spherical object with about 10-12 layers and a gyration radius ∼2.5-2.8 nm. In a vacuum, 42% show just one 5-fold symmetry axis, 33% adopt a defected icosahedral arrangement, and 25% lose all 5-fold symmetry and display a face-centred-cubic shape with several parallel stacking faults. We model a constrained version of the same assembly that takes place between two Au(111) surfaces. During the dynamics, the two Au(111) surfaces are kept fixed at distances of 55 Å, 55.5 Å, 56 Å, and 56.5 Å. The latter distance accommodates 24 Au layers with no strain, while the others correspond to nominal strains of 1.5%, 2.4%, and 3.3%, respectively. In the constrained assembly, each individual seed tends to reorganize into a layered configuration, but the filament may break. The probability of breaking the assembled nanofilament depends on the individual morphology of the seeds. It is more likely to break at the decahedron/icosahedron interface, whilst it is more likely to layer with respect to the (111) orientation when a truncated octahedron sits between the decahedron and the icosahedron. We further observe that nanofilaments between surfaces at 56 Å have a >90% probability of breaking, which decreases to 8% when the surfaces are 55 Å apart. We attribute the dramatic change in probability of breaking to the peculiar decahedron/icosahedron interface and the higher average atomic strain in the nanofilaments. This in silico experiment can shed light on the understanding and control of the formation of metallic nanowires and nanoparticle-assembled networks, which find applications in next-generation electronic devices, such as resistive random access memories and neuromorphic devices.

Iodine passivation facilitates on-surface synthesis of robust regular conjugated two-dimensional organogold networks on Au(111).

Two-dimensional conjugated organogold networks with anthra-tetrathiophene repeat units are synthesized by thermally activated debrominative coupling of 2,5,9,12-tetrabromoanthra[1,2-b:4,3-b':5,6-b'':8,7-b''']tetrathiophene (TBATT) precursor molecules on Au(111) surfaces under ultra-high vacuum (UHV) conditions. Performing the reaction on iodine-passivated Au(111) surfaces promotes formation of highly regular structures, as revealed by scanning tunneling microscopy (STM). In contrast, coupling on bare Au(111) surfaces results in less regular networks due to the simultaneous expression of competing intermolecular binding motifs in the absence of error correction. The carbon-Au-carbon bonds confer remarkable robustness to the organogold networks, as evidenced by their high thermal stability. In addition, as suggested by density functional theory (DFT) calculations and underscored by scanning tunneling spectroscopy (STS), the organogold networks exhibit a small electronic band gap in the order of 1.0 eV due to their high π-conjugation.

Correction: Exploring the potential as molecular quantum-dot cellular automata of a mixed-valence Ru2 complex deposited on a Au(111) surface

Correction for ‘Exploring the potential as molecular quantum-dot cellular automata of a mixed-valence Ru2 complex deposited on a Au(111) surface’ by Nicolás Montenegro-Pohlhammer et al., Inorg. Chem. Front., 2023, 10, 2484–2492, https://doi.org/10.1039/D2QI02647C.

Theoretical insights into the interplay between metal-organic and covalent bonding in single-layer molecular networks formed by halogen dissociation.

Synthesis via dehalogenative coupling due to thermal annealing is one of the most common routes of growing metal-organic and covalent polymer networks on catalytic metal surfaces. We present a computational approach taking into account both metal-coordinated and covalent C-C bonding interactions, which drive the self-assembly of tetrabrominated polyarene molecules into single-layer ordered and disordered nanostructures. The proposed coarse-grained lattice model is simulated using the Monte Carlo method. We investigate the annealing effect in ensembles of nearly and fully dehalogenated molecules, accordingly decreasing the concentration of dissociated (chemisorbed) halogen atoms, to account for the desorption process. The results suggest that dissociated halogens may be at least partially responsible for fragmentation of metal-organic networks on the Cu and Au surfaces. The simulations also show that fragmented covalent networks are mostly disordered or characterized by short-range glass-like order, but larger domains of these phases can be obtained after removing the split off Br atoms. We additionally examine the potential formation of fragments with a hybrid structure consisting of oligomer chains linked side-to-side by metal adatoms.

Shearing-induced formation of Au nanowires.

Shearing-induced nucleation is known in our daily lives, yet rarely discussed in nano-synthesis. Here, we demonstrate an unambiguous shearing-induced growth of Au nanowires. While in static solution Au would predominately deposit on pre-synthesized triangular nanoplates to form nano-bowls, the introduction of stirring or shaking gives rise to nanowires, where an initial nucleation could be inferred. Under specific growth conditions, CTAB is responsible for stabilizing the growth materials and the resulting oversaturation promotes shearing-induced nucleation. At the same time, all Au surfaces are passivated by ligands, so that the growth materials are diverted to relatively fresher sites. We propose that the different degrees of "focused growth" in active surface growth could be represented by watersheds of different slopes, so that the subtle differences between neighbouring sites would set course to opposite pathways, with some sites becoming ever more active and others ever more inhibited. The shearing-induced nuclei, with their initially ligand-deficient surface and higher accessibility to growth materials, win the dynamic inter-particle competition against other sites, explaining the dramatic diversion of growth materials from the seeds to the nanowires.

Water at electrode-electrolyte interfaces: combining HOD vibrational spectra with ab initio-molecular dynamics simulations.

We have undertaken a vibrational study of the structure of interfacial water and its potential dependence using H2O : D2O mixtures to explore the O-H and O-D stretching modes of HOD as well as the bending modes of HOD and H2O. Due to the symmetry reduction, some of the complexity characteristic of the vibrational spectrum of water is removed in HOD. Coupled with potential-dependent ab initio simulations of the gold-water interface, this has enabled a deeper insight into the hydrogen-bond network of interfacial water and into how it is affected by the applied potential. Possibly the most important conclusions of our work are (i) the absence of any ice-like first layer of interfacial water at any potential and (ii) that interfacial water reorients around a stable backbone of hydrogen bonds roughly parallel to the electrode surface. At E > pzc, interfacial water molecules are oriented with the oxygen lone pairs towards the surface and form exclusively or nearly exclusively hydrogen-donating hydrogen bonds with other water molecules. At E < pzc, the oxygen lone pairs instead point away from the surface, but the population of hydrogen-donating water molecules does not vanish. In fact, the population of hydrogen-accepting water molecules only dominates at considerably negative charge densities, due to the weak interaction of the hydrogen atoms of interfacial water molecules with the Au surface.

Molar excess of coordinating N-heterocyclic carbene ligands triggers kinetic digestion of gold nanocrystals.

There has been much interest in evaluating the strength of the coordination interactions between N-heterocyclic carbene (NHC) molecules and transition metal ions, nanocolloids and surfaces. We implement a top-down core digestion test of Au nanoparticles (AuNPs) triggered by incubation with a large molar excess of poly(ethylene glycol)-appended NHC molecules, where kinetic dislodging of surface atoms and formation of NHC-Au complexes progressively take place. We characterize the structure and chemical nature of the generated PEG-NHC-Au complexes using 1D and 2D 1H-13C NMR spectroscopy, supplemented with matrix assisted laser desorption/ionization mass spectrometry, and transmission electron microscopy. We further apply the same test using thiol-modified molecules and find that though etching can be measured the kinetics are substantially slower. We discuss our findings within the classic digestion of transition metal ores and colloids induced by interactions with sodium cyanide, which provides an insight into the strength of coordination between the strong σ-donating (soft Lewis base) NHC and Au surfaces (having a soft Lewis acid character), as compared to gold-to-gold covalent binding.

Enantiopure molecules form apparently racemic monolayers of chiral cyclic pentamers.

Ultra-high vacuum scanning tunneling microscopy (UHV-STM) was used to investigate two related molecules pulse-deposited onto Au(111) surfaces: indoline-2-carboxylic acid and proline (pyrrolidine-2-carboxylic acid). Indoline-2-carboxylic acid and proline form both dimers and C5-symmetric "pinwheel" pentamers. Enantiomerically pure S-(-)-indoline-2-carboxylic acid and S-proline were used, and the pentamer structures observed for both were chiral. However, the presence of apparently equal numbers of 'right-' and 'left-handed' pinwheels is contrary to the general understanding that the chirality of the molecule dictates supramolecular chirality. A variety of computational methods were used to elucidate pentamer geometry for S-proline. Straightforward geometry optimization proved difficult, as the size of the cluster and the number of possible intermolecular interactions produced an interaction potential with multiple local minima. Instead, the Amber force field was used to exhaustively search all of phase space for chemically reasonable pentamer structures, producing a limited number of candidate structures that were then optimized as gas-phase clusters using density functional theory (DFT). The binding energies of the two lowest-energy pentamers on the Au(111) surface were then calculated by plane-wave DFT using the VASP software, and STM images predicted. These calculations indicate that the right- and left-handed pentamers are instead two different polymorphs.

Tracking the surface structure and the influence of cations and anions on the double-layer region of a Au(111) electrode.

We examined the electric double-layer (EDL) of a Au(111) electrode in a dilute perchloric acid solution using a combination of capacitance measurements and in situ scanning tunnelling microscopy under electrochemical conditions (ECSTM). The "camel-shaped" capacitance curve of the EDL is studied with different cations and anions, including their impact on the potential of zero charge (PZC). We show that the ECSTM images of thermally reconstructed and of the potential-induced surface reconstruction of Au(111) in perchloric acid electrolyte resemble previous work in sulphuric acid, displaying a herringbone pattern for a thermally reconstructed surface. Once the reconstruction is lifted, the Au(111) forms islands with an average of 1 atomic step height. When the potential is lowered below that of the PZC, the potential-induced surface reconstruction results in a more disoriented pattern than the thermally reconstructed surface. ECSTM images at different potentials are correlated with the voltammogram to understand the time and potential dependence of the surface. This correlation has led to the development of a potential window technique that can be used to reveal the surface structure of Au(111) based on observing the changes in PZC in the voltammogram. This method provides an indirect approach to understanding the surface structure without always relying on ECSTM. From the voltammogram, we also observed that anions (SO42-, CH3SO3-, ClO4-, F-) interact more strongly with the Au(111) surface than the alkali cations. The cation capacitance peak shape does not depend strongly on the identity of the alkali metal cation (Li+, Na+, K+). However, the anion capacitance peak depends strongly on the anion identity. It suggests that some level of specific adsorption cannot be excluded, even for anions that are traditionally not considered to adsorb specifically (perchlorate, fluoride).

Voltage-induced modulation of the magnetic exchange in binuclear Fe(III) complex deposited on Au(111) surface.

We present a complete computational study devoted to the deposition of a magnetic binuclear complex on a metallic surface, aimed to obtain insight into the interaction of magnetically coupled complexes with their supporting substrates, as well as their response to external electrical stimuli applied through a surface-molecule-STM molecular junction-like architecture. Our results not only show that the deposition is favorable in two of the four studied orientations, but also, that the magnetic coupling is only slightly perturbed once the complex is adsorbed. We observe that the effects of the applied bias voltage on the magnetic coupling strongly depend on the molecule orientation with respect to the surface and the voltage polarity. Further analysis shows that this behavior is attributable to the stabilization/destabilization of the d-type singly occupied orbitals of the iron centers, reinforced by the strong local electric fields and induced charge densities only present in certain orientations of the deposited molecule and applied voltage polarity.