Au@Pt Dendrimer Encapsulated Nanoparticles As Model Electrocatalysts for Comparison of Experiment and Theory

In this paper we report the electrochemical synthesis of core@shell dendrimer-encapsulated nanoparticles (DENs) consisting of cores containing 147 Au atoms (Au-147) and Pt shells having similar to 54 or similar to 102 atoms (Au-147@Pt-n (n = 54 or 102)). The significance of this work arises from the correlation of the experimentally determined structural and electrocatalytic properties of these particles with density functional theory (DFT) calculations. Specifically, we describe an experimental and theoretical study of Pb underpotential deposition (UPD) on Au-147 DENs, the structure of both Au-147@Pb-n and Au-147@Pt-n DENs, and the activity of these DENs for the oxygen reduction reaction (ORR). DFT calculations show that Pb binding is stronger on the (100) facets of Au as compared to (111), and the calculated deposition and stripping potentials are consistent with those measured experimentally. Galvanic exchange is used to replace the surface Pb atoms with Pt, and a surface distortion is found for Au-147@Pt-n particles using molecular dynamics simulations in which the Pt-covered (100) facets shear into (111) diamond structures. DFT calculations of oxygen binding show that the distorted surfaces are the most active for the ORR, and that their activity is similar regardless of the Pt coverage. These calculations are consistent with rotating ring-disk voltammetry measurements.Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U. S. Department of Energy DE-FG02-09ER16090Robert A. Welch Foundation F-0032, F-1601Institute of Computational and Engineering Sciences at UT-AustinChemistr

Finite-Temperature Auxiliary-Field Quantum Monte Carlo for Bose-Fermi Mixtures

We present a quantum Monte Carlo (QMC) technique for calculating the exact finite-temperature properties of Bose-Fermi mixtures. The Bose-Fermi Auxiliary-Field Quantum Monte Carlo (BF-AFQMC) algorithm combines two methods, a finite-temperature AFQMC algorithm for bosons and a variant of the standard AFQMC algorithm for fermions, into one algorithm for mixtures. We demonstrate the accuracy of our method by comparing its results for the Bose-Hubbard and Bose-Fermi-Hubbard models against those produced using exact diagonalization for small systems. Comparisons are also made with mean-field theory and the worm algorithm for larger systems. As is the case with most fermion Hamiltonians, a sign or phase problem is present in BF-AFQMC. We discuss the nature of these problems in this framework and describe how they can be controlled with well-studied approximations to expand BF-AFQMC's reach. The new algorithm can serve as an essential tool for answering many unresolved questions about many-body physics in mixed Bose-Fermi systems.Comment: 19 pages, 6 figure

Direct Evidence for the Source of Reported Magnetic Behavior in "CoTe"

In order to unambiguously identify the source of magnetism reported in recent studies of the Co-Te system, two sets of high-quality, epitaxial CoTe$_x$ films (thickness $\simeq$ 300 nm) were prepared by pulse laser deposition (PLD). X-ray diffraction (XRD) shows that all of the films are epitaxial along the [001] direction and have the hexagonal NiAs structure. There is no indication of any second phase metallic Co peaks (either $fcc$ or $hcp$) in the XRD patterns. The two sets of CoTe$_x$ films were grown on various substrates with PLD targets having Co:Te in the atomic ratio of 50:50 and 35:65. From the measured lattice parameters $c = 5.396 \AA$ for the former and $c = 5.402\AA$ for the latter, the compositions CoTe$_{1.71}$ (63.1% Te) and CoTe$_{1.76}$ (63.8% Te), respectively, are assigned to the principal phase. Although XRD shows no trace of metallic Co second phase, the magnetic measurements do show a ferromagnetic contribution for both sets of films with the saturation magnetization values for the CoTe$_{1.71}$ films being approximately four times the values for the CoTe$_{1.76}$ films. $^{59}$Co spin-echo nuclear magnetic resonance (NMR) clearly shows the existence of metallic Co inclusions in the films. The source of weak ferromagnetism reported in several recent studies is due to the presence of metallic Co, since the stoichiometric composition "CoTe" does not exist.Comment: 19 pages, 7 figure

Interacting Attention-gated Recurrent Networks for Recommendation

Capturing the temporal dynamics of user preferences over items is important for recommendation. Existing methods mainly assume that all time steps in user-item interaction history are equally relevant to recommendation, which however does not apply in real-world scenarios where user-item interactions can often happen accidentally. More importantly, they learn user and item dynamics separately, thus failing to capture their joint effects on user-item interactions. To better model user and item dynamics, we present the Interacting Attention-gated Recurrent Network (IARN) which adopts the attention model to measure the relevance of each time step. In particular, we propose a novel attention scheme to learn the attention scores of user and item history in an interacting way, thus to account for the dependencies between user and item dynamics in shaping user-item interactions. By doing so, IARN can selectively memorize different time steps of a user's history when predicting her preferences over different items. Our model can therefore provide meaningful interpretations for recommendation results, which could be further enhanced by auxiliary features. Extensive validation on real-world datasets shows that IARN consistently outperforms state-of-the-art methods.Comment: Accepted by ACM International Conference on Information and Knowledge Management (CIKM), 201

Characterization of severe fever with thrombocytopenia syndrome in rural regions of Zhejiang, China.

Severe fever with thrombocytopenia syndrome virus (SFTSV) infections have recently been found in rural regions of Zhejiang. A severe fever with thrombocytopenia syndrome (SFTS) surveillance and sero-epidemiological investigation was conducted in the districts with outbreaks. During the study period of 2011-2014, a total of 51 SFTSV infection cases were identified and the case fatality rate was 12% (6/51). Ninety two percent of the patients (47/51) were over 50 years of age, and 63% (32/51) of laboratory confirmed cases occurred from May to July. Nine percent (11/120) of the serum samples from local healthy people without symptoms were found to be positive for antibodies to the SFTS virus. SFTSV strains were isolated by culture using Vero, and the whole genomic sequences of two SFTSV strains (01 and Zhao) were sequenced and submitted to the GenBank. Homology analysis showed that the similarity of the target nucleocapsid gene from the SFTSV strains from different geographic areas was 94.2-100%. From the constructed phylogenetic tree, it was found that all the SFTSV strains diverged into two main clusters. Only the SFTSV strains from the Zhejiang (Daishan) region of China and the Yamaguchi, Miyazakj regions of Japan, were clustered into lineage II, consistent with both of these regions being isolated areas with similar geographic features. Two out of eight predicted linear B cell epitopes from the nucleocapsid protein showed mutations between the SFTSV strains of different clusters, but did not contribute to the binding ability of the specific SFTSV antibodies. This study confirmed that SFTSV has been circulating naturally and can cause a seasonal prevalence in Daishan, China. The results also suggest that the molecular characteristics of SFTSV are associated with the geographic region and all SFTSV strains can be divided into two genotypes