A chemically consistent graph architecture for massive reaction networks applied to solid-electrolyte interphase formation

Modeling reactivity with chemical reaction networks could yield fundamental mechanistic understanding that would expedite the development of processes and technologies for energy storage, medicine, catalysis, and more. Thus far, reaction networks have been limited in size by chemically inconsistent graph representations of multi-reactant reactions (e.g. A + B → C) that cannot enforce stoichiometric constraints, precluding the use of optimized shortest-path algorithms. Here, we report a chemically consistent graph architecture that overcomes these limitations using a novel multi-reactant representation and iterative cost-solving procedure. Our approach enables the identification of all low-cost pathways to desired products in massive reaction networks containing reactions of any stoichiometry, allowing for the investigation of vastly more complex systems than previously possible. Leveraging our architecture, we construct the first ever electrochemical reaction network from first-principles thermodynamic calculations to describe the formation of the Li-ion solid electrolyte interphase (SEI), which is critical for passivation of the negative electrode. Using this network comprised of nearly 6000 species and 4.5 million reactions, we interrogate the formation of a key SEI component, lithium ethylene dicarbonate. We automatically identify previously proposed mechanisms as well as multiple novel pathways containing counter-intuitive reactions that have not, to our knowledge, been reported in the literature. We envision that our framework and data-driven methodology will facilitate efforts to engineer the composition-related properties of the SEI – or of any complex chemical process – through selective control of reactivity.

A chemically consistent graph architecture enables autonomous identification of novel solid-electrolyte interphase formation pathways from a massive reaction network.     

Longitudinal nuclear relaxation measurements in hcp H2

Measurements of T₁ in the hep phase of H₂, over the temperature range 2°–12°K and the ortho concentration range between 0.5 and 0.97 are presented. At temperatures below 10°K, the thermally activated self-diffusion is negligible and the mechanism for nuclear relaxation is that attributed by Moryia and Motizuki and by Harris to intramolecular dipolar interaction, modulated by intennolecular electric quadrupole-quadrupole (EQQ) interaction. The gaussian approximation for the correlation function was used by these authors to predict T₁. From the comparison between experiment and theory, we determine the EQQ parameter Γ/k_B to be 0.67°K. Above 10°K the effect of diffusion influences T₁, and the experimental results for an 88 per cent ortho H₂ sample up to the melting point suggest that the relaxation mechanisms resulting from EQQ interaction and diffusion are not independent of one another.     

Projective Modules over the Non-Commutative Sphere

The positive cone of the K₀-group of the non-commutative sphereB is explicitly determined by means of the four basic unboundedtrace functionals discovered by Bratteli, Elliott, Evans andKishimoto. The C*-algebra B is the crossed product A x Z₂ ofthe irrational rotation algebra A by the flip automorphism defined on the canonical unitary generators U, V by (U) = U*,(V) = V*, where VU = e²ⁱ UV and is an irrational real number.This result combined with Rieffel's cancellation techniquesis used to show that cancellation holds for all finitely generatedprojective modules over B. Subsequently, these modules are determinedup to isomorphism as finite direct sums of basic modules. Italso follows that two projections p and q in a matrix algebraover B are unitarily equivalent if, and only if, their vectortraces are equal: [p] = [q]. These results will have the following ramifications. They areused (elsewhere) to show that the flip automorphism on A isan inductive limit automorphism with respect to the basic buildingblock construction of Elliott and Evans for the irrational rotationalgebra. This will, in turn, yield a two-tower proof of thefact that B is approximately finite dimensional, first provedby Bratteli and Kishimoto.     

Planar graphs,Hamilton cycles and extreme independence number

If a graph has too many edges, it must be Hamiltonian. We show how to construct graphs near the threshold: they have as many edges as possible without sacrificing planarity but are not Hamiltonian. We base our construction on the concepts of independent sets and 1-toughness.The work of the author was partially supported by CNPq-Brasil.     

R andRτ ratios at the five-loop level of perturbative QCD

We study perturbative QCD at the five-loop level. In particular we considerR = _tot(e ⁺ e ^– hadrons)/(e ⁺ e ^{– + –}) andR = ( v+hadrons)/( ev). We use our method to estimate the five-loop coefficients. As a result, we obtain _s (M _z ) = 0.1186(11) and _s (34 GeV) = 0.1396(16), which are accurate at the 1% level. We also findR = 3.8350(18), which is consistent withR and is accurate to 0.05%.     

Cutting planes,connectivity, and threshold logic

Originating from work in operations research the cutting plane refutation systemCP is an extension of resolution, where unsatisfiable propositional logic formulas in conjunctive normal form are recognized by showing the non-existence of boolean solutions to associated families of linear inequalities. Polynomial sizeCP proofs are given for the undirecteds-t connectivity principle. The subsystemsCP _q ofCP, forq2, are shown to be polynomially equivalent toCP, thus answering problem 19 from the list of open problems of [8]. We present a normal form theorem forCP ₂-proofs and thereby for arbitraryCP-proofs. As a corollary, we show that the coefficients and constant terms in arbitrary cutting plane proofs may be exponentially bounded by the number of steps in the proof, at the cost of an at most polynomial increase in the number of steps in the proof. The extensionCPLE ⁺, introduced in [9] and there shown top-simulate Frege systems, is proved to be polynomially equivalent to Frege systems. Lastly, since linear inequalities are related to threshold gates, we introduce a new threshold logic and prove a completeness theorem.Supported in part by NSF grant DMS-9205181 and by US-Czech Science and Technology Grant 93-205Partially supported by NSF grant CCR-9102896 and by US-Czech Science and Technology Grant 93-205     

Aurifeuillian factorizations and the period of the Bell numbers modulo a prime

We show that the minimum period modulo of the Bell exponential integers is for all primes and several larger . Our proof of this result requires the prime factorization of these periods. For some primes the factoring is aided by an algebraic formula called an Aurifeuillian factorization. We explain how the coefficients of the factors in these formulas may be computed.