Rate constant for deuterium atom recombination calculated by the orbiting resonance theory

Resonance theory for three body recombination kinetics for calculating recombination rate constant of deuterium ato

Metabolic network percolation quantifies biosynthetic capabilities across the human oral microbiome

The biosynthetic capabilities of microbes underlie their growth and interactions, playing a prominent role in microbial community structure. For large, diverse microbial communities, prediction of these capabilities is limited by uncertainty about metabolic functions and environmental conditions. To address this challenge, we propose a probabilistic method, inspired by percolation theory, to computationally quantify how robustly a genome-derived metabolic network produces a given set of metabolites under an ensemble of variable environments. We used this method to compile an atlas of predicted biosynthetic capabilities for 97 metabolites across 456 human oral microbes. This atlas captures taxonomically-related trends in biomass composition, and makes it possible to estimate inter-microbial metabolic distances that correlate with microbial co-occurrences. We also found a distinct cluster of fastidious/uncultivated taxa, including several Saccharibacteria (TM7) species, characterized by their abundant metabolic deficiencies. By embracing uncertainty, our approach can be broadly applied to understanding metabolic interactions in complex microbial ecosystems.T32GM008764 - NIGMS NIH HHS; T32 GM008764 - NIGMS NIH HHS; R01 DE024468 - NIDCR NIH HHS; R01 GM121950 - NIGMS NIH HHS; DE-SC0012627 - Biological and Environmental Research; RGP0020/2016 - Human Frontier Science Program; NSFOCE-BSF 1635070 - National Science Foundation; HR0011-15-C-0091 - Defense Advanced Research Projects Agency; R37DE016937 - NIDCR NIH HHS; R37 DE016937 - NIDCR NIH HHS; R01GM121950 - NIGMS NIH HHS; R01DE024468 - NIDCR NIH HHS; 1457695 - National Science FoundationPublished versio

Origin of the structural phase transition in Li7La3Zr2O12

Garnet-type Li7La3Zr2O12 (LLZO) is a solid electrolyte material with a low-conductivity tetragonal and a high-conductivity cubic phase. Using density-functional theory and variable cell shape molecular dynamics simulations, we show that the tetragonal phase stability is dependent on a simultaneous ordering of the Li ions on the Li sublattice and a volume-preserving tetragonal distortion that relieves internal structural strain. Supervalent doping introduces vacancies into the Li sublattice, increasing the overall entropy and reducing the free energy gain from ordering, eventually stabilizing the cubic phase. We show that the critical temperature for cubic phase stability is lowered as Li vacancy concentration (dopant level) is raised and that an activated hop of Li ions from one crystallographic site to another always accompanies the transition. By identifying the relevant mechanism and critical concentrations for achieving the high conductivity phase, this work shows how targeted synthesis could be used to improve electrolytic performance

Kinetics of the Thermal Decomposition of Dimethylmercury. I. Cyclopentane Inhibition

The kinetics of the pyrolysis of gaseous dimethylmercury have been studied in the presence and absence of cyclopentane inhibitor from 290–375°C for the inhibited and 265–350°C for the uninhibited reactions. The decomposition in excess cyclopentane is first order, with methane the major product (accounting for >95% of the carbon). Rate constants are dependent upon the ratio of dimethylmercury (DMM) to cyclopentane and upon total pressure. The constant for DMM loss is: kD=1.1×1015 exp(—55 900/RT) sec—1. The rate constant (from combined data on DMM loss and CH4 formation) extrapolated to the fully inhibited, high‐pressure limit is: k1=5.0×1015 exp(—57 900/RT) sec—1.The data for the uninhibited decomposition agree with the literature; a partial mechanism is suggested which predicts the transition from chain to nonchain behavior with increasing temperature.For the inhibited reaction the following mechanism is proposed: (1) Hg(CH3)2→HgCH3+CH3, (2) HgCH3→Hg+CH3, (3) CH3+Hg(CH3)2→CH4+CH3HgCH2, (4) CH3+C5H10→CH4+C5H9, (5) CH3+Hg(CH3)2→C2H6+HgCH3, (6) 2 CH3→C2H6, (7) CH3HgCH2→HgCH3+CH2.Using the present value of E1=57.9±1.4 kcal/mole in conjunction with known thermochemical data, E2=0±3 kcal/mole. From the inhibition data, k3/k4=0.7±0.2 at 300°C, with a very small temperature coefficient. The inert gas pressure effect is evidence for the unimolecular nature of step (1).Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/70105/2/JCPSA6-30-3-607-1.pd

Kinetics of the Thermal Decomposition of Dimethylmercury. II. Carbon‐13 Isotope Effect

The C13 kinetic isotope effect in the pyrolysis of gaseous dimethylmercury has been studied in the presence and absence of cyclopentane inhibitor from 290–375°C for the inhibited and 290–350°C for the uninhibited reactions. The isotopic fractionation factor (S) is defined as the ratio of rate constants for the decomposition of Hg(C12H3)2 vs C12H3HgC13H3. S shows a strong dependence upon the degree of inhibition of the methyl radical chain, which, in turn, is a function of the ratio of cyclopentane to dimethylmercury. S is also a function of the total pressure.The dependence of S upon the degree of inhibition agrees quantitatively with the predictions of the mechanism proposed in I. The pressure effect on the isotope effect is attributed to the unimolecular nature of the rate determining step (Hg☒C bond rupture) and is consistent with the over‐all kinetics.The isotope rate factor in the fully inhibited high‐pressure limit, α, is 1.034±0.002 (essentially independent of temperature over the range studied), compared to a value of 1.011±0.001 for the uninhibited (chain) decomposition.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/71109/2/JCPSA6-30-3-613-1.pd

From Electrons to Finite Elements: A Concurrent Multiscale Approach for Metals

We present a multiscale modeling approach that concurrently couples quantum mechanical, classical atomistic and continuum mechanics simulations in a unified fashion for metals. This approach is particular useful for systems where chemical interactions in a small region can affect the macroscopic properties of a material. We discuss how the coupling across different scales can be accomplished efficiently, and we apply the method to multiscale simulations of an edge dislocation in aluminum in the absence and presence of H impurities.Comment: 4 page

Globular Cluster Abundances from High-Resolution Integrated Light Spectra, I: 47 Tuc

We describe the detailed chemical abundance analysis of a high-resolution (R~35,000), integrated-light (IL), spectrum of the core of the Galactic globular cluster 47 Tuc, obtained using the du Pont echelle at Las Campanas. We develop an abundance analysis strategy that can be applied to spatial unresolved extra- galactic clusters. We have computed abundances for Na, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Ba, La, Nd and Eu. For an analysis with the known color-magnitude diagram (cmd) for 47 Tuc we obtain a mean [Fe/H] value of -0.75 +/-0.026+/-0.045 dex (random and systematic error), in good agreement with the mean of 5 recent high resolution abundance studies, at -0.70 dex. Typical random errors on our mean [X/Fe] ratios are 0.07-0.10 dex, similar to studies of individual stars in 47 Tuc, although Na and Al appear enhanced, perhaps due to proton burning in the most luminous cluster stars. Our IL abundance analysis with an unknown cmd employed theoretical Teramo isochrones; however, we apply zero-point abundance corrections to account for the factor of 3 underprediction of stars at the AGB bump luminosity. While line diagnostics alone provide only mild constraints on the cluster age (ruling-out ages younger than ~2 Gyr), when theoretical IL B-V colors are combined with metallicity derived from the Fe I lines, the age is constrained to 10--15 Gyr and we obtain [Fe/H]=-0.70 +/-0.021 +/-0.052 dex. We find that Fe I line diagnostics may also be used to constrain the horizontal branch morphology of an unresolved cluster. Lastly, our spectrum synthesis of 5.4 million TiO lines indicates that the 7300-7600A TiO window should be useful for estimating the effect of M giants on the IL abundances, and important for clusters more metal-rich than 47 Tuc.Comment: 40 pages text & references, 4 tables, 19 figures (72 pages total). Changes include addition of B-V color to help constrain GC age. To appear in Ap

Third-order cosmological perturbations of zero-pressure multi-component fluids: Pure general relativistic nonlinear effects

Present expansion stage of the universe is believed to be mainly governed by the cosmological constant, collisionless dark matter and baryonic matter. The latter two components are often modeled as zero-pressure fluids. In our previous work we have shown that to the second-order cosmological perturbations, the relativistic equations of the zero-pressure, irrotational, multi-component fluids in a spatially near flat background effectively coincide with the Newtonian equations. As the Newtonian equations only have quadratic order nonlinearity, it is practically interesting to derive the potential third-order perturbation terms in general relativistic treatment which correspond to pure general relativistic corrections. Here, we present pure general relativistic correction terms appearing in the third-order perturbations of the multi-component zero-pressure fluids. We show that, as in a single component situation, the third-order correction terms are quite small (~ 5 x10^{-5} smaller compared with the relativistic/Newtonian second-order terms) due to the weak level anisotropy of the cosmic microwave background radiation. Still, there do exist pure general relativistic correction terms in third-order perturbations which could potentially become important in future development of precision cosmology. We include the cosmological constant in all our analyses.Comment: 20 pages, no figur

Anti-Proton Evolution in Little Bangs and Big Bang

The abundances of anti-protons and protons are considered within momentum-integrated Boltzmann equations describing Little Bangs, i.e., fireballs created in relativistic heavy-ion collisions. Despite of a large anti-proton annihilation cross section we find a small drop of the ratio of anti-protons to protons from 170 MeV (chemical freeze-out temperature) till 100 MeV (kinetic freeze-out temperature) for CERN-SPS and BNL-RHIC energies thus corroborating the solution of the previously exposed "ani-proton puzzle". In contrast, the Big Bang evolves so slowly that the anti-baryons are kept for a long time in equilibrium resulting in an exceedingly small fraction. The adiabatic path of cosmic matter in the phase diagram of strongly interacting matter is mapped out