Surface ligands influence the selectivity of cation uptake in polyoxovanadate–alkoxide clusters
Surface modification of polyoxovanadate–alkoxide clusters influences selectivity for Li + in electrochemically induced cation uptake.
Garwick, Rachel E.↗
SEARCH · Engineering Papers
Results for “clusters”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Uniform titania-supported Ce( iii ) carbonate cluster catalysts for degradation of reactive oxygen species
Uniform 2.5 nm Ce( iii ) carbonate clusters on TiO 2 function as ROS degradation catalysts, consistent with a superoxide dismutase–catalase tandem reaction mechanism.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Metal–support interactions in metal oxide-supported atomic, cluster, and nanoparticle catalysis
Supported metal catalysts are essential to a plethora of processes in the chemical industry. The overall performance of these catalysts depends strongly on the interaction of adsorbates at the atomic level, which can be manipulated and controlled by the different constituents of the active material (i.e., support and active metal). The description of catalyst activity and the relationship between active constituent and the support, or metal–support interactions (MSI), in heterogeneous (thermo)catalysts is a complex phenomenon with multivariate (dependent and independent) contributions that are difficult to disentangle, both experimentally and theoretically. So-called “strong metal–support interactions” have been reported for several decades and summarized in excellent review articles. However, in recent years, there has been a proliferation of new findings related to atomically dispersed metal sites, metal oxide defects, and, for example, the generation and evolution of MSI under reaction conditions, which has led to the designation of (sub)classifications of MSI deserving to be critically and systematically evaluated. These include dynamic restructuring under alternating redox and reaction conditions, adsorbate-induced MSI, and evidence of strong interactions in oxide-supported metal oxide catalysts. Here, we review recent literature on MSI in oxide-supported metal particles to provide an up-to-date understanding of the underlying physicochemical principles that dominate the observed effects in supported metal atomic, cluster, and nanoparticle catalysts. Critical evaluation of different subclassifications of MSI is provided, along with discussions on the formation mechanisms, theoretical and characterization advances, and tuning strategies to manipulate catalytic reaction performance. We also provide a perspective on the future of the field, and we discuss the analysis of different MSI effects on catalysis quantitatively.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Activation and electrochemical reduction of carbon dioxide by transition metal atom-doped copper clusters
Doping transition metals in Cu 13 clusters enhance CO 2 reduction by altering electronic and magnetic properties, lowering overpotentials by ∼20%.
Mohanta, Manish Kumar [Department of Physics, Virg↗
Electronic energy transfer ionization in naphthalene–CO 2 clusters reveals excited states of dry ice
Vacuum ultraviolet excitation of CO 2 clusters and concomitant energy transfer to naphthalene leads to ionization which provides an understanding of excited state chemistry relevant to astrochemistry.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Atomically precise surface chemistry of zirconium and hafnium metal oxo clusters beyond carboxylate ligands
Computational and experimental investigation of metal oxo cluster surface chemistryvialigand exchange reactions with phosphinic and phosphonic acid ligands.
Chemistry↗
Efficient urea synthesis via one-step N–C–N coupling: strong metal–support interaction-driven planar Cu clusters on two-dimensional Mo 2 C MXene
The anchoring of the Cu cluster on Mo 2 C substrate can achieve a planar configuration, effectively boosting urea synthesisviaa one-step mechanism.
Chemistry↗
Iron Cluster Encapsulated N-Doped Single-Walled Carbon Nanotubes as ORR Electrocatalyst: A First-Principles Study
The ORR electrocatalytic activities of N-doped single-walled nanotubes infused with Fe7 clusters are assessed with DFT calculations. The incorporation of Fe7 leads to enhanced activity and stability via electron donation. The models presented in this work propose a promising strategy for designing non-precious metal ORR catalysts.
Fu, Yuqing [UC Riverside]↗
Quasar clustering at redshift 6
Large-scale surveys over the last years have revealed about 300 quasi-stellar objects (QSOs) at redshifts above 6. Follow-up observations have identified surprising properties, such as the very high black hole (BH) masses, spatial correlations with surrounding cold gas of the host galaxy, and high CIV-MgII Velocity shifts. In particular, the discovery of luminous high-redshift quasars suggests that at least some BHs likely have high masses at birth and grow efficiently. Our aim is to quantify quasar pairs at high redshift for a large sample of objects. This provides a new key constraint on a combination of parameters related to the origin and assembly for the most massive BHs: formation efficiency and clustering, growth efficiency, and the relative contribution of BH mergers. We observed 116 spectroscopically confirmed QSOs around redshift 6 with the simultaneous seven-channel imager Gamma-ray Burst Optical/Near-infrared Detector in order to search for companions. Applying colour-colour cuts identical to those which led to the spectroscopically confirmed QSOs, we performed Le PHARE fits to the 26 best QSO pair candidates, and obtained spectroscopic observations for 11 of them. We do not find any QSO pair with a companion brighter than M 1450 (AB) < –26 mag within our 0.1–3.3 h –1 cMpc search radius, in contrast to the serendipitous findings in the redshift range 4–5. However, a small fraction of such pairs at this luminosity and redshift is consistent with indications from present-day cosmological-scale galaxy evolution models. In turn, the incidence of L- and T-type brown dwarfs, which occupy a similar colour space to z ~ 6 QSOs, is higher than expected, by a factor of 5 and 20, respectively.
79 ASTRONOMY AND ASTROPHYSICS↗
Experience with dynamic resource provisioning of the CMS online cluster using a cloud overlay
The primary goal of the online cluster of the Compact Muon Solenoid (CMS) experiment at the Large Hadron Collider (LHC) is to build event data from the detector and to select interesting collisions in the High Level Trigger (HLT) farm for offline storage. With more than 1500 nodes and a capacity of about 850 kHEPSpecInt06, the HLT machines represent similar computing capacity of all the CMS Tier1 Grid sites together. Moreover, it is currently connected to the CERN IT datacenter via a dedicated 160 Gbps network connection and hence can access the remote EOS based storage with a high bandwidth. In the last few years, a cloud overlay based on OpenStack has been commissioned to use these resources for the WLCG when they are not needed for data taking. This online cloud facility was designed for parasitic use of the HLT, which must never interfere with its primary function as part of the DAQ system. It also allows to abstract from the different types of machines and their underlying segmented networks. During the LHC technical stop periods, the HLT cloud is set to its static mode of operation where it acts like other grid facilities. The online cloud was also extended to make dynamic use of resources during periods between LHC fills. These periods are a-priori unscheduled and of undetermined length, typically of several hours, once or more a day. For that, it dynamically follows LHC beam states and hibernates Virtual Machines (VM) accordingly. Finally, this work presents the design and implementation of a mechanism to dynamically ramp up VMs when the DAQ load on the HLT reduces towards the end of the fill.
97 MATHEMATICS AND COMPUTING↗
Development of alpha cluster structure in nuclei of the same mass number
The resonant 14 N+α particle scattering was studied in the 18 F excitation region from 6.5 to 9 MeV at Astana cyclotron using the TTIK approach. The excitation functions for the elastic 14 N+α scattering were analyzed in the framework of R-matrix approach. The observed strong alpha cluster structure in 18 F is compared with that in 18 O.
Nurmukhanbetova, Aliya↗
Modeling radiative-shocks created by laser–cluster interactions
Radiative-shocks induced by laser–cluster interactions are modeled using radiation-hydrodynamic simulations. A good agreement—in both shock velocity and density profiles—is obtained between experiment and simulations, indicating that non-local thermodynamic equilibrium (NLTE) radiative effects are important in the experimental regime examined, particularly at early times (≤30 ns) due to the elevated temperatures (≥35 eV). The enhanced NLTE radiative emission causes the shock to be reduced in amplitude, increased in width, and reduced in propagation velocity, while the amplitude of the radiative precursor is increased. As the density and temperature conditions are relatively modest, this potentially has important implications for the scalings that are used in laboratory–astrophysics to transform between laboratory and astrophysical scales, which do not hold for non-LTE systems.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Effective Hamiltonians derived from equation-of-motion coupled-cluster wave functions: Theory and application to the Hubbard and Heisenberg Hamiltonians
Effective Hamiltonians, which are commonly used for fitting experimental observables, provide a coarse-grained representation of exact many-electron states obtained in quantum chemistry calculations; however, the mapping between the two is not trivial. In this contribution, we apply Bloch’s formalism to equation-of-motion coupled-cluster (EOM-CC) wave functions to rigorously derive effective Hamiltonians in the Bloch’s and des Cloizeaux’ forms. We report the key equations and illustrate the theory by application to systems with two or three unpaired electrons, which give rise to electronic states of covalent and ionic characters. We show that the Hubbard and Heisenberg Hamiltonians can be extracted directly from the so-obtained effective Hamiltonians. By establishing a quantitative connection between many-body states and simple models, the approach facilitates the analysis of the correlated wave functions. We propose a simple diagnostic for assessing the validity of the model space choice based on the overlaps between the target- and model-space states. Finally, artifacts affecting the quality of electronic structure calculations such as spin contamination are also discussed.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Equation of motion coupled-cluster cumulant approach for intrinsic losses in x-ray spectra
We present an equation of motion coupled cluster approach for calculating and understanding intrinsic inelastic losses in core level x-ray absorption spectra (XAS). The method is based on a factorization of the transition amplitude in the time-domain, which leads to a convolution of an effective one-body spectrum and the core-hole spectral function. The spectral function characterizes these losses in terms of shake-up excitations and satellites, and is calculated using a cumulant representation of the core-hole Green’s function that includes non-linear corrections. The one-body spectrum also includes orthogonality corrections that enhance the XAS at the edge.
Rehr, John J.↗
The influence of lattice defects, recombination, and clustering on thermal transport in single crystal thorium dioxide
Thermal transport is a key controlling property for thorium dioxide in many applications where defect-generating radiation fields are present. An understanding of the effect of nanoscale lattice defects on thermal transport in this material is currently unavailable due to a lack of high-quality, single crystal material from which unit processes may be investigated. In this work, a series of thorium dioxide single crystals are exposed to 2 MeV proton irradiation at room temperature and 600°C to create microscale regions with varying densities and types of point and extended defects. Defected regions are investigated using spatial domain thermoreflectance to quantify the change in thermal conductivity as a function of ion fluence as well as transmission electron microscopy and Raman spectroscopy to interrogate the structure of the generated defects. Together, this com- bination of methods provides important initial insight into defect formation, recombination, and clustering in thorium dioxide and the effect of those defects on thermal transport. These methods also provide a promising pathway for the quantification of the smallest-scale defects which cannot be captured using traditional microscopy techniques and play and outsized role in degrading thermal performance.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Coupled cluster benchmarks of large noncovalent complexes: The L7 dataset as well as DNA–ellipticine and buckycatcher–fullerene
In this work, benchmark binding energies for dispersion-bound complexes in the L7 dataset, the DNA–ellipticine intercalation complex, and the buckycatcher–C60 complex with 120 heavy atoms using a focal-point method based on the canonical form of second-order Møller−Plesset theory (MP2) and the domain based local pair natural orbital scheme for the coupled cluster with single, double, and perturbative triple excitations [CCSD(T)] extrapolated to the complete basis set (CBS) limit are reported. This work allows for increased confidence given the agreement with respect to values recently obtained using the local natural orbital CCSD(T) for L7 and the canonical CCSD(T)/CBS result for the coronene dimer (C2C2PD). Therefore, these results can be considered pushing the CCSD(T)/CBS binding benchmark to the hundred-atom scale. The disagreements between the two state-of-the-art methods, CCSD(T) and fixed-node diffusion Monte Carlo, are substantial with at least 2.0 (∼10%), 1.9 (∼5%), and 10.3 kcal/mol (∼25%) differences for C2C2PD in L7, DNA–ellipticine, and buckycatcher–C60, respectively. Such sizable discrepancy above “chemical accuracy” for large noncovalent complexes indicates how challenging it is to obtain benchmark binding interactions for systems beyond small molecules, although the three up-to-date density functionals, PBE0+D4, ωB97M-V, and B97M-V, agree better with CCSD(T) for these large systems. In addition to reporting these values, different basis sets and various CBS extrapolation parameters for Hartree–Fock and MP2 correlation energies were tested for the first time in large noncovalent complexes with the goal of providing some indications toward optimal cost effective routes to approach the CBS limit without substantial loss in quality.
Ballesteros, Francisco (ORCID:0000000325732307)↗
GPU acceleration of rank-reduced coupled-cluster singles and doubles
Here, we have developed a graphical processing unit (GPU) accelerated implementation of our recently introduced rank-reduced coupled-cluster singles and doubles (RR-CCSD) method. RR-CCSD introduces a low-rank approximation of the doubles amplitudes. This is combined with a low-rank approximation of the electron repulsion integrals via Cholesky decomposition. The result of these two low-rank approximations is the replacement of the usual fourth-order CCSD tensors with products of second- and third-order tensors. In our implementation, only a single fourth-order tensor must be constructed as an intermediate during the solution of the amplitude equations. Owing in large part to the compression of the doubles amplitudes, the GPU-accelerated implementation shows excellent parallel efficiency (95% on eight GPUs). Our implementation can solve the RR-CCSD equations for up to 400 electrons and 1550 basis functions—roughly 50% larger than the largest canonical CCSD computations that have been performed on any hardware. In addition to increased scalability, the RR-CCSD computations are faster than the corresponding CCSD computations for all but the smallest molecules. We test the accuracy of RR-CCSD for a variety of chemical systems including up to 1000 basis functions and determine that accuracy to better than 0.1% error in the correlation energy can be achieved with roughly 95% compression of the ov space for the largest systems considered. We also demonstrate that conformational energies can be predicted to be within 0.1 kcal mol -1 with efficient compression applied to the wavefunction. Finally, we find that low-rank approximations of the CCSD doubles amplitudes used in the similarity transformation of the Hamiltonian prior to a conventional equation-of-motion CCSD computation will not introduce significant errors (on the order of a few hundredths of an electronvolt) into the resulting excitation energies.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Coupled Cluster Downfolding Methods: the effect of double commutator terms on the accuracy of ground-state energies
Downfolding coupled cluster (CC) techniques have recently been introduced into quantum chemistry as a tool for the dimensionality reduction of the many-body quantum problem. As opposed to earlier formulations in physics and chemistry based on the concept of effective Hamiltonians, the appearance of the downfolded Hamiltonians is a natural consequence of the single-reference exponential parametrization of the wave function. In this paper, we discuss the impact of higher-order terms originating in double commutators. In analogy to previous studies, we consider the case when only one- and two-body interactions are included in the downfolded Hamiltonians. We demonstrate the efficiency of the many-body expansions involving single and double commutators for the unitary extension of the downfolded Hamiltonians on the example of the beryllium atom, and bond-breaking processes in the Li2 and H2O molecules. For the H2O system, we also analyze energies obtained with downfolding procedures as functions of the active space size.
quantum computing, quantum algorithms, electronic ↗