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All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Nanotwin stability in alloyed copper under ambient and cryo-temperature dependent deformation states

Nanometer size grains, solid solution strengthening, low temperatures, and a high density of nanotwins can provide significant strengthening to a material. Nevertheless, under loading the microstructure may evolve altering the effect of grain size, twin density, etc. on this strengthening. In some cases, these effects can be coupled as in detwinning, which is a mechanism for cryogenic grain growth. Here, in this work, a series of copper nanotwinned columnar grains are solid solution alloyed with aluminum and subject to ambient and cryogenic (–196 °C) environments during mechanical indentation, with the influence of alloying on the detwinning evolution studied. Under indentation, at a lower aluminum solute content (2 at.%), the columnar grains bent corresponding to a loss of twins. At a higher aluminum solute content (8 at.%), the grains shear and retain the nanotwins. Atomistic-scale simulations reveal an increase in the incoherent twin boundary velocity with decreasing temperature, but this boundary velocity is reduced with increasing alloy solute content. The coupling of solid solution strengthening and nanotwin stabilization is then used to explain the microstructural stability as a function of indentation at different temperature conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Extending Interfaces in 3D to Achieve Superior Nanoscale Strength in Ti/Nb Nanolaminates

Tuning the atomic-level structure of nanolaminates enables high strength, increased deformability, and the ability to absorb and mitigate damage due to varied crystalline defects, including dislocations. Here, we present the enhanced strength of Ti/Nb nanolaminates containing thick 3D interfaces (3DIs), relative to their chemically abrupt 2D counterparts. We examine the effects of crystallographic alignment and compositional gradients on mechanical behavior via experiments and phase-field-dislocation dynamics (PFDD) modeling. Mechanical testing reveals that nanolaminates containing thicker 3DIs demonstrate a 28% hardness enhancement compared with sharp-interface nanolaminates. PFDD modeling shows that the critical resolved shear stress (CRSS) increases with the 3DI thickness. Gradual compositional transitions in 3DIs were confirmed via scanning transmission electron microscopy and high-resolution transmission electron microscopy, showing sharp crystallographic transitions and a heightened interface topography. The findings establish a positive function between the 3DI thickness and mechanical robustness for hexagonal-closest-packed-containing composites, emphasizing the role of defect–interface interactions in tailoring the mechanical performance and providing a foundation for future interfacial engineering.

36 MATERIALS SCIENCE↗
NASA NTRS2004

Residual Strength Characterization of a Curved Integrally-Stiffened Panel

Over the years, Finite-element fracture simulation methodology has been very well established at NASA Langley to predict the residual strength of damaged aircraft structures. This methodology has been experimentally verified at NASA Langley for structures ranging from laboratory coupons up to full-scale built-up structural components with single and multiple-site damage cracking. The methodology uses the critical crack-tip-opening-angle (CTOA) fracture criterion to characterize the fracture behavior of the material. The CTOA fracture criterion assumes that stable crack growth occurs when the crack-tip angle reaches a constant critical value. The use of the CTOA criterion requires an elastic-plastic, finite-element analysis. The critical CTOA value is determined by simulating fracture behavior in laboratory specimens, such as a compact specimen, to obtain the angle that best fits the observed test behavior. The critical CTOA value appears to be independent of loading, crack length, and in-plane dimensions. However, it is a function of material thickness and local crack-front constraint. Modeling the local constraint requires either a three-dimensional analysis or a two-dimensional analysis with an approximation to account for the constraint effects. In recent times as the aircraft industry is leaning towards monolithic structures with the intension of reducing part count and manufacturing cost, there has been a consistent effort at NASA Langley to extend critical CTOA based numerical methodology in the analysis of integrally-stiffened panels. In this regard, a series of fracture tests were conducted on curved aluminum-alloy integrally-stiffened panels. These curved panels were subjected to uniaxial tension and pressure loading. During the test, applied load-crack extension, out-of-plane displacements and local deformations around the crack tip region were measured. Compact and middle-crack tension specimens were tested to determine the critical angle (psi(sub c) using three-dimensional code (ZIP3D) and the plane-strain core height (h(sub c)) using two-dimensional code (STAGS).

Seshadri, B. R.↗
NASA NTRS2022

A Numerical Study of the Liquid Motion in Titan’s Subsurface Ocean

An ocean filled with liquid water lies beneath the icy surface of several Jovian and Saturnian moons. In such an ocean, the currents are driven by various phenomena such as the tidal forcing, the deformation of the ice shell lying at its top, the temperature gradient resulting from the surface and bottom heat fluxes…The flow induced by the first two forcings can be modelled by means of a 2D depth-averaged model, while the third one generates horizontal and vertical density variations whose effects can only be captured by a 3D baroclinic model. We study the tides of Titan’s subsurface ocean and the impact of the ice shell on the liquid motion by means of the Second-generation Louvain-la-Neuve Ice–ocean Model, SLIM (https://www.climate.be/slim). The impact of the ice shell lying at the top of the ocean is modelled by a surface friction term and surface pressure terms. The latter are a function of the difference between the ocean elevation and the vertical displacement of the shell and the time derivative of this difference. Because of Titan’s appreciable obliquity (0.306°), the tidal motion expected (and found) is similar to the Europa tidal scenario described by Tyler (2008): the surface elevation consists of two bulges rotating around Titan and the associated depth-averaged velocity field consists of two gyres, separated by an area of high speed flow, whose centre follows a sinusoidal path centred on the equator. The ice shell damps the surface motion, thus slowing down the flow, without significantly modifying the spatial patterns of these fields. The depth of the ocean and the mechanical characteristics of the ice shell being poorly constrained, a sensitivity analysis is conducted. The depth-averaged flow slows down when the depth is increased and a lag appears in the tidal phase but the tidal range remains similar. The ice shell mechanical characteristics influences both the elevation and depth-averaged velocity fields in terms of magnitude but does not modify the spatial patterns of these fields. The influence of the surface heat flux is studied by means of the 3D baroclinic version of SLIM. The heat flux derived from Titan’s topography by Kvorka et al. (2018) is used as surface boundary condition for the temperature equation while a uniform bottom heat flux is implemented. Its value is computed assuming that the heat budget of the ocean is at equilibrium. These boundary conditions cause density variations, which impact the hydrodynamics of the ocean. While the flow velocity induced by these variations is two orders of magnitude smaller than the tidal flow, its orientation is time-independent, hence impacting the orientation of the velocity field. Although the variations of ocean surface elevation and speed with respect to the shell mechanical properties can be larger than those induced by the surface heat flux, taking into account the latter results in large variations of the velocity field global patterns, which was not observed when modifying the shell mechanical properties. Future studies should therefore focus on modelling the surface and bottom heat fluxes while uncertainties about the mechanical characteristics of the shell can be tolerated.

Titan↗
DOE OSTI2024

Optoelectronic properties of bent two-dimensional materials from first-principles methods combined with machine learning

A material’s interaction with light is highly relevant in the design of nanoelectronic devices such as photodiodes, solar cells, photocatalytic cells, phototransistors, and photodetectors. The interaction of a material with light can be altered by mechanical deformation. Fine tuning of the optical properties can be achieved by mechanical bending that alters the electronic structure. Optical properties strongly depend on band gaps, therefore any alteration in the band structure results in a changed optical response of the material. The impact of bending was explored in this project. The goal of this project was to assess the impact of mechanical bending of two-dimensional transition metal dichalcogenides on their optoelectronic properties, using first-principles methods. These first-principles approximations are largely built upon many-body theory for the optical properties of magnetic and topological nanoribbons. GW-BSE is standard for optical absorption, but it is less practical for collective excitations as it was shown in model systems. Time-dependent density functional theory, however, has better promises for collective excitations in low-dimensional materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Unveiling the origins of work-hardening enhancement and mechanical instability in laser shock peened titanium

Laser shock-peening (LSP) produces complex gradients in microstructures and residual stresses, which enables fabrication of metallic engineering components with superior mechanical properties. In this work, we use non-destructive and spatially resolved high-energy X-ray diffraction (HE-XRD) to investigate the influences of LSP on microstructure, surface topography, and residual stress for high purity titanium plates. LSP is found to produce large compressive in-plane residual stresses near the peened surface which monotonically decay to zero about 2.5 mm below the surface. These properties were also tracked during in-situ tensile loading, allowing stress partitioning and work-hardening rates to be measured as a function of depth. The surface region is found to have the highest work-hardening rate and remain mechanically stable up to sample failure. In addition, a crystal rigid rotation along a transversal axis of about 27 & nbsp; was observed at large applied strain near the surface region, which is attributed to the formation of denser dispersed shear bands. Furthermore, a sudden drop in tensile stress was observed at a depth of similar to 160 mu m from the LSP surface, indicating the formation of a localized mechanical instability zone (LMIZ). The origin of this LMIZ could be attributed to the increase in shear stress induced by a load transfer from LSP surface due to the formation of denser dispersed shear bands. These observations indicate a localized transition in deformation behavior has occurred from dispersed shear banding to LMIZ and homogeneous deformation.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Metal Bellows Valve Reliability Testing - Copper Stem Tip Testing

SRNL was funded in Mid-Year FY20 by NNSA NA-231 to continue evaluation of alternate valves for use in tritium service to support domestic Mo-99 production. The focus of the effort was to identify valve cycle life as a function of actuator size and stem tip material. Using the minimum size actuator to reliability open and close valves can reduce glovebox size and thus support domestic companies to “come to market” faster in supplying Mo-99 to the US market. This report serves as a continuation to the FY19 report and summarizes the task activities completed in FY20 after authorization to start work was obtained on May 5 th , 2020. Copper stem tips were tested on the Swagelok 1C and 5C actuated metal bellows valves. With ambitions to cycle each set 150,000 times, both 1C and 5C valves were met with high failure rates. The smaller 1C actuated valves required additional closing pressure to form a seal with the Cu stem tips installed however, excessive stem tip deformation may be the root cause of the majority of the valves failing before 500 cycles. The larger 5C actuated valves were cycled 150,000 times but still resulted in 80% failure rate, suspected of metal fatigue in the bellows due to high cycling frequencies.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Flexible CO 2 Sensor Architecture with Selective Nitrogen Functionalities by One‐Step Laser‐Induced Conversion of Versatile Organic Ink

Abstract Nitrogen‐containing carbons (NC) are a class of sustainable materials for selective CO 2 adsorption. A versatile concept is introduced to fabricate flexible NC‐based sensor architectures for room‐temperature sensing of CO 2 in a one‐step laser conversion of primary films cast from abundant precursors. By the unidirectional energy impact in conjunction with depth‐dependent attenuation of the laser beam, a layered sensor heterostructure with a porous transducer and active sensor layer is formed. Comprehensive microscopic and spectroscopic cross‐sectional analyses confirm the preservation of the high content of imidazolic nitrogen in the sensor. The performance is optimized in terms of material morphology, chemical composition, and surface chemistry to achieve a linear relative resistive response of up to Δ R / R 0 = −14.3% (10% of CO 2 ). Thermodynamic analysis yields Δ ads H values of −35.6 and 34.1 kJ·mol −1 for H 2 O and CO 2 , respectively. The sensor is operable even in humid environments (e.g., ∆ R / R 0,RH = 80% = 0.53%) and shows good performance upon strong mechanical deformation.

flexible gas sensors↗
NASA NTRSDate not supplied

Organic-rich fluids in Pluto’s interior—A source of cryovolcanic activity

The highly variegated surface of Pluto revealed by the New Horizons spacecraft is composed of both volatile ices (N2, CH4, CO) and H2O ice, all of which are intrinsically colorless. The colors on Pluto reveal a non-ice component generally acknowledged to be a refractory complex organic material (tholins) produced by photolysis in the planet’s atmosphere [1], and by photolysis and radiolysis of the surface ices [2-4]. These processes have produced a range of colors from pale yellow to red to brown, and result in a variation of a factor of 10in albedo across the surface. Tholins are disordered polymer-like materials made of repeating chains of linked subunits and complex combinations of functional groups containing carbon. Nitrogen, oxygen, and other elements can be substituted in both the aliphatic and aromatic subunits. The detection of the spectral absorption of an ammoniated compound associated with surface exposures of red-colored H2O ice (herein, RAW) in the LEISA spectral mapping data from New Horizons suggests that a third source of a colored material is ejected from Pluto’s interior as a water-rich fluid(cryomagma) that rapidly freezes at the low temperature (~40K) of the surface [5,6]. The ammoniated compound is thought to be an ammonia hydrate or an ammoniated salt; the spectral data cover a limited wavelength range, resulting in ambiguity in the identification of the form of the ammonia. The distribution of RAW in the vicinity of tectonically stressed and deformed geological structures, particularly graben (fossae), is seen as the result of both fluid effusion and fountaining ejection of cryoclastic materials in Pluto’s Virgil Fossae region [5,6]. RAW is seen elsewhere on Pluto, both in association with graben complexes and on broad expanses of old surface, but primarily in zones of tectonic stress. The nature of the putative subsurface fluid is unknown, but it must have existed at relatively shallow depths such that the graben faulting could reach it. Geochemical modeling of fluids in the interiors of small planetary bodies in the outer Solar System[7] shows that ammonia-bearing H2O in contact with rock and metal components produce a rich chemical soup, including gases that can, in principle, help propel the fluid from shallow reservoirs through crustal fractures to reach the surface. An organic component of the fluid cryomagma is predicted to originate from thermal processing of the components [ref] and may be an example of one-pot synthesis of such complexes as amino acid precursors [ref].

Dale P Cruikshank↗
DOE OSTI2019

Fragility of Fermi arcs in Dirac semimetals

We use tunable, vacuum ultraviolet laser based angle-resolved photoemission spectroscopy and density functional theory (DFT) calculations to study the electronic properties of Dirac semimetal candidate cubic PtBi 2 . In addition to bulk electronic states we also find surface states in PtBi 2 , which is expected as PtBi 2 was theoretically predicated to be a candidate Dirac semimetal. The surface states are also well reproduced from DFT band calculations. Impressively, the topological surface states form Fermi contours rather than double Fermi arcs that were observed in Na 3 Bi. The surface bands forming the Fermi contours merge with bulk bands in proximity to the Dirac point projections, as expected. Our data validate the existence of Dirac states in PtBi 2 and reveal the fragility of the Fermi arcs in Dirac semimetals. Because the Fermi arcs are not topologically protected in general, they can be deformed into Fermi contours, as proposed by M. Kargarian et al. [Proc. Natl. Acad. Sci. USA 113, 8648 (2016)]. Our results demonstrate the validity of this theory in PtBi 2 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS2008

A Verification-Driven Approach to Control Analysis and Tuning

This paper proposes a methodology for the analysis and tuning of controllers using control verification metrics. These metrics, which are introduced in a companion paper, measure the size of the largest uncertainty set of a given class for which the closed-loop specifications are satisfied. This framework integrates deterministic and probabilistic uncertainty models into a setting that enables the deformation of sets in the parameter space, the control design space, and in the union of these two spaces. In regard to control analysis, we propose strategies that enable bounding regions of the design space where the specifications are satisfied by all the closed-loop systems associated with a prescribed uncertainty set. When this is unfeasible, we bound regions where the probability of satisfying the requirements exceeds a prescribed value. In regard to control tuning, we propose strategies for the improvement of the robust characteristics of a baseline controller. Some of these strategies use multi-point approximations to the control verification metrics in order to alleviate the numerical burden of solving a min-max problem. Since this methodology targets non-linear systems having an arbitrary, possibly implicit, functional dependency on the uncertain parameters and for which high-fidelity simulations are available, they are applicable to realistic engineering problems..

Crespo, Luis G.↗
DOE OSTI2024

Multiscale simulation of spatially correlated microstructure via a latent space representation

When deformation gradients act on the scale of the microstructure of a part due to geometry and loading, spatial correlations and finite-size effects in simulation cells cannot be neglected. We propose a multiscale method that accounts for these effects using a variational autoencoder to encode the structure–property map of the stochastic volume elements making up the statistical description of the part. In this paradigm the autoencoder can be used to directly encode the microstructure or, alternatively, its latent space can be sampled to provide likely realizations. Furthermore, we demonstrate the method on three examples using the common additively manufactured material AlSi10Mg in: (a) a comparison with direct numerical simulation of the part microstructure, (b) a push forward of microstructural uncertainty to performance quantities of interest, and (c) a simulation of functional gradation of a part with stochastic microstructure.

Elastoplasticity↗
NASA NTRS1997

A Viscoplastic Constitutive Theory for Monolithic Ceramic Materials

With increasing use of ceramic materials in high temperature structural applications such as advanced heat engine components, the need arises to accurately predict thermomechanical behavior. This paper, which is the first of two in a series, will focus on inelastic deformation behavior associated with these service conditions by providing an overview of a viscoplastic constitutive model that accounts for time-dependent hereditary material deformation (e.g., creep, stress relaxation, etc.) in monolithic structural ceramics. Early work in the field of metal plasticity indicated that inelastic deformations are essentially unaffected by hydrostatic stress. This is not the case, however, for ceramic-based material systems, unless the ceramic is fully dense. The theory presented here allows for fully dense material behavior as a limiting case. In addition, ceramic materials exhibit different time-dependent behavior in tension and compression. Thus, inelastic deformation models for ceramics must be constructed in a fashion that admits both sensitivity to hydrostatic stress and differing behavior in tension and compression. A number of constitutive theories for materials that exhibit sensitivity to the hydrostatic component of stress have been proposed that characterize deformation using time-independent classical plasticity as a foundation. However, none of these theories allow different behavior in tension and compression. In addition, these theories are somewhat lacking in that they are unable to capture creep, relaxation, and rate-sensitive phenomena exhibited by ceramic materials at high temperature. When subjected to elevated service temperatures, ceramic materials exhibit complex thermomechanical behavior that is inherently time-dependent, and hereditary in the sense that current behavior depends not only on current conditions, but also on thermo-mechanical history. The objective of this work is to present the formulation of a macroscopic continuum theory that captures these time-dependent phenomena. Specifically, the overview contained in this paper focuses on the multiaxial derivation of the constitutive model, and examines the scalar threshold function and its attending geometrical implications.

Janosik, Lesley A.↗
NASA NTRS1993

Calculation of AGARD Wing 445.6 Flutter Using Navier-Stokes Aerodynamics

The flutter characteristics of the first AGARD standard aeroelastic configuration for dynamic response, Wing 445.6, are studied using an unsteady Navier-Stokes algorithm in order to investigate a previously noted discrepancy between Euler flutter characteristics and the experimental data. The algorithm, which is a three-dimensional, implicit, upwind Euler/Navier-Stokes code (CFL3D Version 2.1), was previously modified for the time-marching, aeroelastic analysis of wings using the unsteady Euler equations. These modifications include the incorporation of a deforming mesh algorithm and the addition of the structural equations of motion for their simultaneous time integration with the governing flow equations. In this paper, the aeroelastic method is extended and evaluated for applications that use the Navier- Stokes aerodynamics. The paper presents a brief description of the aeroelastic method and presents unsteady calculations which verify this method for Navier-Stokes calculations. A linear stability analysis and a time-marching aeroelastic analysis are used to determine the flutter characteristics of the isolated 45 deg. swept-back wing. Effects of fluid viscosity, structural damping, and number of modes in the structural model are investigated. For the linear stability analysis, the unsteady generalized aerodynamic forces of the wing are computed for a range of reduced frequencies using the pulse transfer-function approach. The flutter characteristics of the wing are determined using these unsteady generalized aerodynamic forces in a traditional V-g analysis. This stability analysis is used to determine the flutter characteristics of the wing at free-stream Mach numbers of 0.96 and 1.141 using the generalized aerodynamic forces generated by solving the Euler equations and the Navier-Stokes equations. Time-marching aeroelastic calculations are performed at a free-stream Mach number of 1.141 using the Euler and Navier-Stokes equations to compare with the linear V-g flutter analysis method. The V-g analysis, which is used in conjunction with the time-marching analysis, indicates that the fluid viscosity has a significant effect on the supersonic flutter boundary for this wing while the structural damping and number of modes in the structural model have a lesser effect.

Lee-Rausch, Elizabeth M.↗
DOE OSTI2018

Time-Dependent Consolidation in Porous Geomaterials at In Situ Conditions of Temperature and Pressure

Analysis of quartz sandstones shows that grain-scale crushing (fracture and rearrangement) and associated sealing of fractures contribute significantly to consolidation. The crushing strength (P*) for granular material is defined by laboratory experiments conducted at strain rates of 10 -4 to 10 -5 s -1 and room temperature. Based on experiments, many sandstones would require burial depths in excess of the actual maximum burial depth to create observed microstructure and density. In this paper, we use experiments and soil mechanics principles to determine rate laws for brittle consolidation of fine-grained quartz sand to better estimate in situ failure conditions of porous geomaterials. Experiments were conducted on St. Peter sand utilizing different isostatic consolidation and creep load paths at temperatures to 200 °C and at strain rates of 10 -4 to 10 -10 s -1 . Experiment results are consistent with observed rate dependence of consolidation in soils, and P* for sand can be identified by the change in the dependence of consolidation rate with stress, allowing the extrapolation of P* determined in the laboratory to geologic rates and temperatures. Additionally, normalized P* values can be described by a polynomial function to quantify temperature, stress, and strain-rate relationships for the consolidation of porous geomaterials by subcritical cracking. At geologic loading rates, P* for fine-grained quartz sand is achieved within ~3-km burial depth, and thus, shear-enhanced compaction under nonisostatic stress can occur at even shallower depths. Finally, these results demonstrate that time and temperature effects must be considered for predicting the brittle consolidation of sediments in depositional basins, petroleum reservoirs, and engineering applications.

58 GEOSCIENCES↗
DOE OSTI2020

Interplay between Intrinsic Thermal Stability and Expansion Properties of Functionalized UiO-67 Metal–Organic Frameworks

The UiO family of metal-organic frameworks (MOFs) has been extensively studied for several applications owing to their high stability rendered by their robust secondary building units. The efficient design and use of these materials require a fundamental understanding of their thermal stability and its impact on chemical and structural functionality. In this work, we provide a detailed characterization of the intrinsic thermal behavior of the UiO-67 and functional analogues, UiO-67-NH 2 and UiO-67-CH 3 . Using in situ temperature-programmed X-ray diffraction, we find that distortion of the carboxylate group on the organic linker leads to negative thermal expansion (NTE) of the UiO-67 MOFs during heating. This NTE behavior is correlated with rich and reversible thermal changes observed in the MOF infrared spectral signature as samples are heated to the sample activation temperature (473 K). We find that in the absence of oxygen, activated UiO-67 samples show higher thermal stability compared to ambient or inert environments, with temperature-programmed desorption revealing an overall stability trend: UiO-67 > UiO-67- CH 3 > UiO-67-NH 2 . Two stages of change are observed during thermal treatment above 473 K, which are directly related to deformation of the inorganic node and the isotropic NTE behavior of these materials. Ultimately, these results provide a real-time interpretation of the fundamental thermoresponsive behavior of UiO-67 MOFs and offer a foundation for accurate interpretation of MOF interactions with guest molecules and their temperature dependence.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Bilayer phosphorene under high pressure: in situ Raman spectroscopy

In this study, bilayer phosphorene samples were subjected to high pressure using a Diamond Anvil Cell (DAC) and their vibrational properties were studied via in situ Raman spectroscopy. Systematic shifting in the Raman frequency of A 1 g , B 2 g , and A 2 g modes was observed and theoretical calculations were performed to understand the relationship between the strain and the vibrational properties. The changes in the vibration modes under high pressure are found to reflect the deformation in the structure and its stiffness. Firstly, the study shows a substantial pressure-induced enhancement of the interactions between atoms for the out-plane mode A 1 g , mainly due to the directional nature of the lone pair of electrons and charge transfer. However, these interactions and the observed blue shift of the A 1 g Raman peak are much weaker than those in bulk black phosphorous. Secondly, while a significant enhancement of the atomic interactions due to bond length change is also observed for the in-plane mode B 2 g along the zigzag direction, there is almost negligible effect on the in-plane mode A 2 g along the armchair direction. The results add to the knowledge on mechanical properties and strain engineering in phosphorene towards novel functionalities and applications of this intriguing two-dimensional (2D) material.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Understanding the interaction between carboxylates and coinage metals from first principles

Carboxylate groups have recently been explored as a new type of ligand to protect superatomic copper and silver nanoclusters, but little is known of the interfacial structure and bonding. Here, we employ density functional theory to investigate the interfaces of a model carboxylate group, CH3COO, on the coinage metal surfaces and clusters. We found that μ2-CH3COO is the most preferred binding mode on the three M(111) surfaces (M = Cu, Ag, and Au), while μ3-CH3COO is also stable on Cu(111) and Ag(111). The saturation coverage was found to be about seven CH3COO groups per nm2 for all surfaces. CH3COO has the strongest binding on Cu and weakest on Au. Moving from the flat surfaces to the icosahedral M13 clusters, we found that the eight-electron superatomic [M13(CH3COO)6]− nanoclusters also prefer the μ2-CH3COO mode on the surface. The icosahedral kernel in [Cu13(CH3COO)6]− and [Ag13(CH3COO)6]− was well maintained after geometry optimization, but a larger deformation was found in [Au13(CH3COO)6]−. Given the broad availability and variety of carboxylic acids including amino acids, our work suggests that carboxylate groups could be the next-generation ligands to further expand the universe of atomically precise metal clusters, especially for Cu and Ag.

Liu, Tongyu↗