Au Chains Research Articles

Computational study of conductance through Cu, Ag, Au and Pt atomic chain contacts

Atomic size wires are basic devices of molecular electronics and a common model for simulation of transport properties of other molecular devices, where hypothetical semi-infinite equidistant atomic chains are considered as electrodes. In this work, structure of infinite linear Cu, Ag, Au and Pt atomic chains was studied at nonrelativistic, scalar and spin–orbit zeroth order relativistic approximation levels. Bonds in chains were characterized within Quantum Theory of “Atoms In Molecules” approach. Conductance through finite chains of six atom length between bulk leads for bias voltage range of 0.0–1.0 V was calculated within non-equilibrium Green’s function approach combined with density functional theory. Chain conductance at high bias voltages correlates with product of Jenkins’ metallicity and positively defined kinetic energy density at bond critical points of corresponding infinite atomic chains. Variation of number of atoms in finite Au and Pt chains showed weak “odd-even” oscillations of chain conductance at some bias voltages.

Alteration of the inter-chain distance between Au atomic wires on Si(111) induced by Tl adsorption

Thallium (Tl) deposition onto the Au/Si(111)5 × 2 reconstruction followed by annealing at about 300 °C has been found to result in the formation of the surface structure having 4 × 2 periodicity. Similar to the most reconstructions in the (Au, Tl)/Si(111) system, Au and Tl do not intermix uniformly. While Au chains preserve their inner structure, Tl atoms being highly mobile at room temperature continuously migrate over the Si chains. Thallium donates electrons into the surface, that results in the two consequences: (i) filling the originally partially filled surface-state band, thus converting the metallic surface into an insulating state; (ii) transforming Si chains, which separate Au atomic rows, from the honeycomb-like to the zigzag according to the electron counting rule. The latter alters the inter-chain distance within the array of Au atomic wires. Au and/or Si chains contain point defects, which are masqueraded by the mobile Tl atoms producing peculiar “wavy” STM images.

Solvation‐Mediated Self‐Assembly from Crystals to Helices of Protic Acyclic Carbene AuI‐Enantiomers with Chirality Amplification

AbstractConstructing chiral supramolecular assembly and exploring the underlying mechanism are of great significance in promoting the development of circularly polarized luminescence (CPL)‐active materials. Herein, we report a solvation‐mediated self‐assembly from single‐crystals to helical nanofibers based on the first protic acyclic (methoxy)(amino)carbenes (pAMACs) AuI‐enantiomers driven by a synergetic aurophilic interactions and H‐bonds. Their aggregation‐dependent thermally activated delayed fluorescence properties with high quantum yields (ΦFL) up to 95 % were proved to be attributed to packing modes of Au⋅⋅⋅Au dimers with π‐stacking or one‐dimensional extended Au⋅⋅⋅Au chains. Via drop‐casting method, supramolecular P‐ or M‐helices were prepared. Detailed studies on the helices demonstrate that formations of extended helical Au⋅⋅⋅Au molecular chains amplify supramolecular chirality, leading to strong CPL with high dissymmetry factor (|glum|=0.030, ΦFL=67 %) and high CPL brightness (BCPL) of 4.87×10−3. Our findings bring new insights into the fabrication of helical structures to improve CPL performance by modifying aurophilic interactions.

Solvation-Mediated Self-Assembly from Crystals to Helices of Protic Acyclic Carbene AuI -Enantiomers with Chirality Amplification.

Constructing chiral supramolecular assembly and exploring the underlying mechanism are of great significance in promoting the development of circularly polarized luminescence (CPL)-active materials. Herein, we report a solvation-mediated self-assembly from single-crystals to helical nanofibers based on the first protic acyclic (methoxy)(amino)carbenes (pAMACs) AuI -enantiomers driven by a synergetic aurophilic interactions and H-bonds. Their aggregation-dependent thermally activated delayed fluorescence properties with high quantum yields (ΦFL ) up to 95 % were proved to be attributed to packing modes of Au⋅⋅⋅Au dimers with π-stacking or one-dimensional extended Au⋅⋅⋅Au chains. Via drop-casting method, supramolecular P- or M-helices were prepared. Detailed studies on the helices demonstrate that formations of extended helical Au⋅⋅⋅Au molecular chains amplify supramolecular chirality, leading to strong CPL with high dissymmetry factor (|glum |=0.030, ΦFL =67 %) and high CPL brightness (BCPL ) of 4.87×10-3 . Our findings bring new insights into the fabrication of helical structures to improve CPL performance by modifying aurophilic interactions.

One-Dimensional Heterobimetallic Au/Ag Coordination Polymer Showing a Selective, Reversible, and Visible Vapor-Chromic Photoluminescent Response toward Methanol.

A heterobimetallic coordination polymer [Au4(dppmt)4(AgCl)2]n (1) incorporating an in situ generated P-S ligand (dppmtH) was synthesized from the solvothermal reaction of Au(tht)Cl, AgCl, and dpppyatc in CH3CN/CH2Cl2 (dppmtH = (diphenylphosphino)methanethiol, tht = tetrahydrothiophene, dpppyatc = N,N-bis((diphenylphosphaneyl)methyl)-N-(pyridin-2-yl)-amino-thiocarbamide). The structure of 1 contains a one-dimensional helical Au-Au chain in which the unique [Au4Ag2S2] cluster units are connected by [Au2(dppmt)2] dimers. Upon excitation at 343 nm, 1 exhibited cyan (495 nm) phosphorescent emission at quantum yield (QY) = 22.3% and τ = 0.78 μs (λex = 375 nm). Coordination polymer 1 exhibited a rapid, selective, reversible, and visible vapor-chromic response on exposure to methanol (MeOH) vapor with its emission shifting to a more intense green (530 nm, λex = 388 nm) with QY = 46.8% and τ = 1.24 μs (λex = 375 nm). A polymethylmethacrylate film containing 1 served as a reversible chemical sensor for the sensitive detection of MeOH in air.

Supramolecular assembly and solvochromic luminescence of a Au(I) complex containing di(4‐pyridylmethyl)aminedithiocarbamate

AbstractThe di(4‐pyridylmethyl)aminedithiocarbamate (DPMACS2) ligand was used to react with (Me2S)AuCl to give a dinuclear complex, [Au(DPMACS2)]2, which shows both intramolecular Au(I)⋅⋅⋅Au(I) distances of 2.741(9)–2.788(1) Å and intermolecular Au(I)···Au(I) contacts of 2.917(5)–3.047(7) Å, leading to 1‐D Au(I) chains in the solid state. In addition, complex [Au(DPMACS2)]2 shows the luminescence at 555 nm at room temperature while excited, and almost no energy shift for the luminescence at 553 nm upon grinding has been observed. In this regard, we further examined the solvochromic luminescence upon grinding with various solvents, and the luminescence is within 549–572 nm. It is noted that the solvochromic luminescence for dichloromethane (566 nm) and 1,2‐dichloroethane (572 nm) has been observed, and the original luminescence at 555 nm can be restored upon solvent loss. Indeed, such red‐shifts for the solvochromic luminescence are most likely due to a decrease in intermolecular Au(I)⋅⋅⋅Au(I) contacts while solvents entering into crystal lattices upon grinding and it is a reversible process upon solvent loss.

Phononic heat conductance of gold atomic contacts: Coherent versus incoherent transport

We present here a theoretical method to determine the phononic contribution to the thermal conductance of nanoscale systems in the phase-coherent regime. Our approach makes use of classical molecular dynamics (MD) simulations to calculate the temperature-dependent dynamical matrix, and the phononic heat conductance is subsequently computed within the Landauer-B\"uttiker formalism with the help of nonequilibrium Green's function techniques. Tailored to nanostructures, crucial steps of force constant and heat transport calculations are performed directly in real space. As compared to conventional density functional theory (DFT) approaches, the advantage of our method is two-fold. First, interatomic interactions can be described with the method of choice. Semiempirical potentials may lead to large computational speedups, enabling the study of much larger systems. Second, the method naturally takes into account the temperature dependence of atomic force constants, an aspect that is ignored in typical static DFT-based calculations. We illustrate our method by analyzing the temperature dependence of the phononic thermal conductance of gold (Au) chains with lengths ranging from 1 to 12 atoms. Moreover, in order to evaluate the importance of anharmonic effects in these atomic-scale wires, we compare the phase-coherent approach with nonequilibrium MD (NEMD) simulations. We find that the predictions of the phase-coherent method and the classical NEMD approach largely agree above the Debye temperature for all studied chain lengths, which shows that heat transport is coherent and that our phase-coherent approach is well suited for such nanostructures.

In Situ TEM Observation of the Atomic Transport Process during the Coalescence of Au Nanoparticles.

In practical applications, the coalescence of metal nanoparticles (NPs) is a major factor affecting their physical chemistry properties. Currently, due to a lack of understanding of the atomic-level mechanisms during the nucleation and growth stages of coalescence, the correlation between the different dynamic factors in the different stages of NP coalescence is unclear. In this study, we used advanced in situ characterization techniques to observe the formation of atomic material transport channels (Au chains) during the initiation of coalescence nucleation. We focused on the movement and migration states of Au atoms and discovered an atomic ordered arrangement growth mechanism that occurs after the completion of nucleation. Simultaneously, we used density functional theory to reveal the formation principle of Au chains. These findings improve our understanding of the atomic-scale coalescence process, which can provide a new perspective for further research on coalescence atomic dynamics.

Simple approach to current-induced bond weakening in ballistic conductors

We present a simple, first principles scheme for calculating mechanical properties of nonequilibrium bulk systems assuming an ideal ballistic distribution function for the electronic states described by the external voltage bias. This allows for fast calculations of estimates of the current-induced stresses inside bulk systems carrying a ballistic current. The stress is calculated using the Hellmann-Feynman theorem, and is in agreement with the derivative of the nonequilibrium free energy. We illustrate the theory and present results for one-dimensional (1D) metal chains. We find that the susceptibility of the yield stress to the applied voltage agrees with the ordering of break voltages among the metals found in experiments. In particular, gold is seen to be the most stable under strong current, while aluminum is the least stable.

Electronic phase transitions in quasi-one-dimensional atomic chains: Au wires on Si(553)

The Si(553) surface, covered with half a monolayer of gold, forms a double strand of well-ordered atomic Au chains in each miniterrace. It represents one of the smallest possible realizations of quasi-one-dimensional (1D) systems. In this prototype system, by combining DC conductance and low-energy electron diffraction measurements with density functional calculations and ab initio Monte Carlo simulations, we demonstrate that nonlocal electronic correlations, together with thermal excitations, lead to peculiar phase transitions without long-range order. They are characterized by marginal (average) geometric relaxations, but with huge variations of the electronic band structure and concomitant strong temperature-dependent modifications of the density of states close to the Fermi level. Similar phenomena are expected in the large class of quasi-1D conductors and open a wide range of possibilities for their controlled manipulation. It is the increasing hybridization between spin-polarized Au and Si edge states that makes the Si dangling bond states at the step edge conducting, first as a transient between two insulating phases and finally opening a permanent new 1D conduction channel at high temperatures.

Adsorbate‐Induced Modifications in the Optical Response of the Si(553)–Au Surface

The conductivity of substrate‐supported metallic nanowires can be adjusted, e.g., by strain or adsorbates. In this article, the effect of atomic hydrogen and toluene‐3,4‐dithiol (TDT) adsorption on the quasi‐1D structures of the Si(553)‐(5 × 2)–Au reconstruction is investigated. Reflectance anisotropy spectroscopy (RAS) and infrared ellipsometry reveal optical signatures of the surface. Spectral modifications related to the adsorbate exposure suggest the activation of adsorption‐induced interband transitions. Density functional theory (DFT) calculations reproduce the spectral modifications and explain their origin. Preferential adsorption on sites located at the step edges of the structure occurs independent of the type of adsorbate and induces a charge transfer between electronic states related to the step edges and the Au dimer rows. This charge redistribution modifies the electronic structure close to the Fermi level, enhances the dimerization of the Au chains, and strongly influences the low‐energy region of the RAS spectra. While previous studies employed atomic H as a chief adsorbate, it is shown here that even molecular H deeply modifies the Si(553)–Au optical response. Structural modification of Au–Si(553) by H and TDT adsorbates as suggested from recent ab initio calculations are verified.

Chiral structures of 6,12-dibromochrysene on Au(111) and Cu(111) surfaces

Nanoscale low-dimensional chiral architectures are increasingly receiving scientific interest, because of their potential applications in many fields such as chiral recognition, separation and transformation. Using 6,12-dibromochrysene (DBCh), we successfully constructed and characterized the large-area two-dimensional chiral networks on Au(111) and one-dimensional metal-liganded chiral chains on Cu(111) respectively. The reasons and processes of chiral transformation of chiral networks on Au(111) were analyzed. We used scanning tunneling spectroscopy (STS) to analyze the electronic state information of this chiral structure. This work combines scanning tunneling microscopy (STM) with non-contact atomic force microscopy (nc-AFM) techniques to achieve ultra-high-resolution characterization of chiral structures on low-dimensional surfaces, which may be applied to the bond analysis of functional nanofilms. Density functional theory (DFT) was used to simulate the adsorption behavior of the molecular and energy analysis in order to verify the experimental results.

Au adsorption on stepped Si(hhk)-Au surfaces

The impact of submonolayer gold adsorption on metallic atomic wires grown on terraced silicon substrates is modeled from first principles. Calculations within density functional theory predict Au adsorption at the Si step edge of the Si(553)-Au surface and moderate mobility of the Au adatoms. Although the Au adsorption at the Si step edge does not substantially modify its geometry, a large adsorbate-to-substrate electronic transfer is predicted, which causes a rearrangement of the electronic band structure. The electronic states related to the Si step edge are shifted below the Fermi energy, while an electronic gap opens between the Au-related electronic states. The gap opening leads to a strong enhancement of the Au-chain dimerization. The Au adsorption at the step edge thus modifies the surface morphology non-locally, as a consequence of the strong electronic correlation in quasi-1D systems. Au adsorption on the Si(775)-Au nanowire system occurs mainly at the Au chain, and then at the Si step edge, instead. Adsorption at the Au chain directly modifies its structure by the formation of a structural defect, while adsorption at the step edge has the same effect as in the case of the Si(553)-Au system.

Plasmon localization by adatoms in gold atomic wires on Si(775)

Self-organized gold chains on vicinal Si(111) surfaces represent prototype examples of quasi-one-dimensional objects that are stabilized by hybridization with Si surface states. Their plasmons contain important information about the unoccupied bandstructure close to the Fermi level. Using Si(775)–Au as an example, we report here the modifications of the plasmon dispersion by the simple atomic adatom species H and O. Using a combination of low energy electron diffraction and high-resolution electron energy loss spectroscopy, we study the interconnection between plasmonic excitation and the corresponding local surface structure. Both adsorbates do not destroy metallicity, but, similar to Si(553)–Au, atomic hydrogen enhances dimerization of the Au chains, which at small concentrations counteracts the disorder introduced by random adsorption. This effect, most likely caused by electron donation of H to the surface states, is missing in case of adsorbed oxygen, so that only the effect of disorder is observed. For both adsorbates increasing disorder as a function of adsorbate concentration finally results in plasmon localization and opening of a band gap.

Surface localized phonon modes at the Si(553)-Au nanowire system

The vibrational properties of the Si(553)-Au surface are studied by Raman spectroscopy and ab initio calculations. A multitude of surface localized phonon modes with wave number below 200 ${\mathrm{cm}}^{\ensuremath{-}1}$ is experimentally observed, along with two modes at about 400 ${\mathrm{cm}}^{\ensuremath{-}1}$. Atomistic models within density functional theory allow to assign the low-energy spectral features to vibrations within the Au chain, while the Raman signatures at higher energies are mostly localized at the Si step edge. The Raman activity of nominally silent modes associated with a large charge transfer between Au chain and Si step edge states is explained by scattering at charge density fluctuations. Temperature-dependent measurements reveal specific mode shifts that are discussed in terms of a recently proposed order-disorder phase transition. The presence of model-specific displacement patterns allows us to identify the structural models compatible with the measured spectra at low and at room temperature.

New Noncentrosymmetric Tetrel Pnictides Composed of Square-Planar Gold(I) with Peculiar Bonding.

Three novel isostructural equiatomic gold tetrel pnictides, AuSiAs, AuGeP, and AuGeAs, were synthesized and characterized. These phases crystallize in the noncentrosymmetric (NCS) monoclinic space group Cc (no. 9), featuring square‐planar Au within cis‐[AuTt2Pn2] units (Tt=tetrel, Si, Ge; Pn=pnictogen, P, As). This is in drastic contrast to the structure of previously reported AuSiP, which exhibits typical linear coordination of Au with Si and P. Chemical bonding analysis through the electron localization function suggests covalent two‐center two‐electron Tt−Pn bonds, and three‐center Au−Tt−Au and Au−Pn−Au bonds with 1.6 e − per bond. X‐ray photoelectron spectroscopy studies support the covalent and nonionic nature of Au−Pn and Au−Tt bonds. The title materials were found to be n‐type narrow‐gap semiconductors or semimetals, with nearly temperature‐independent electrical resistivities and low thermal conductivities. A combination of the semimetallic properties with tunable NCS structure provides opportunities for the development of materials based on gold tetrel pnictides.

Effect of surface interactions on spin contamination errors of homogeneous spin dimers, chains, and films: model calculations of Au/MgO and Au/BaO systems

It is well known that unrestricted density functional theory (UDFT) calculations include spin contamination errors. While errors in UDFT/plane-wave calculations have not been clarified thus far, some effects of these errors are investigated. Recently, our group estimated spin contamination errors in UDFT/plane-wave calculation results by developing and applying the approximate spin projection (AP) scheme [Chem. Phys. Lett., 701: 103 (2018), Mol. Phys., 117: 2251 (2019), Molecules, 24: 505 (2019), Appl. Phys. Express, 12: 115506 (2019)]. In this study, a systematic theoretical investigation of the surface effects on the spin contamination error was performed. For this purpose, we selected model systems such as Au dimers, chains, and film adsorptions onto MgO and BaO (001) surfaces. The calculation results showed the dependence on the dimensions of the supported materials and lattice constants of the supports. In general, the effects of spin contamination errors are decreased by interaction with the surface. The effects of the errors increased by increasing dimension; i.e. the increasing order of spin contamination errors is film > chain > dimer. In addition, the spin-polarised states are stabilised because of the interaction with the surfaces, and spin contamination errors occur in some cases where the Au–Au distances are small.

Comparative Study of Light Guiding by Freestanding Linear Chains of Spherical Au and Si Nanoparticles

Electromagnetic energy guiding by free‐standing straight finite chains of Au and Si spherical nanoparticles is comparatively studied on the basis of a system of integral equations for self‐consistent currents excited inside particles. Self‐consistent currents are given in terms of an electric field T‐scattering tensor (dyadic) operator of a single particle of any shape. Simplifying the T‐scattering operator, the equations system is resolved analytically in the nearest‐neighbor coupling approximation. Interactions beyond the nearest neighbors are accounted for by the perturbative theory. It is shown that electromagnetic excitation propagates along a chain of coupled particles without radiation losses in the form of a dark mode. The resonant conditions for the coupling parameter yield the frequency of the dark mode and the corresponding radius of the particles. As a result, unlike Au chains, no long‐range electromagnetic energy transfer was revealed along the Si chains. Physically, in both cases of Au and Si spheres, the resonant frequencies fall within the bands of the corresponding electric dipole Mie resonances. However, the positive value of the real part of the Si refraction index at the resonant frequency causes exponential excitation currents decreasing with the particle number.

Vibration-Driven Self-Doping of Dangling-Bond Wires on Si(553)-Au Surfaces.

Density-functional theory is used to explore the Si(553)-Au surface dynamics. Our study (i)reveals a complex two-stage order-disorder phase transition where with rising temperature first the ×3 order along the Si step edges and, subsequently, the ×2 order of the Au chains is lost, (ii)identifies the transient modification of the electron chemical potential during soft Au chain vibrations as instrumental for disorder at the step edge, and (iii)shows that the transition leads to a self-doping of the Si dangling-bond wire at the step edge. The calculations are corroborated by Raman measurements of surface phonon modes and explain previous electron diffraction, scanning tunneling microscopy, and surface transport data.

First-principles investigation of monatomic gold wires under tension

Ab initio pseudopotential total-energy calculations on infinite monatomic chains of Au are performed within density functional theory. We use the density functional perturbation theory to study the phonon spectra of these gold wires as a function of strain. Our results show that there does not seem to be a range of strain for which the linear chain is stable, contrary to what was stated by Ribeiro and Cohen [Phys. Rev. B 68 (2003) 035423]. For low strain, the zigzag chain is the stable geometry; while for higher strain, the chains with two or more aligned gold atoms are found to be more stable. At the limit between these two regimes, we predict a transition structure (an asymmetric zigzag chain) to be the most stable.