W4 theory for computational thermochemistry: in pursuit of confident sub-kJ/mol predictions

In an attempt to improve on our earlier W3 theory [J. Chem. Phys. {\bf 120}, 4129 (2004)] we consider such refinements as more accurate estimates for the contribution of connected quadruple excitations ($\hat{T}_4$), inclusion of connected quintuple excitations ($\hat{T}_5$), diagonal Born-Oppenheimer corrections (DBOC), and improved basis set extrapolation procedures. Revised experimental data for validation purposes were obtained from the latest version of the ATcT (Active Thermochemical Tables) Thermochemical Network. We found that the CCSDTQ$-$CCSDT(Q) difference converges quite rapidly with the basis set, and that the formula 1.10[CCSDT(Q)/cc-pVTZ+CCSDTQ/cc-pVDZ$-$CCSDT(Q)/cc-pVDZ] offers a very reliable as well as fairly cost-effective estimate of the basis set limit $\hat{T}_4$ contribution. The largest $\hat{T}_5$ contribution found in the present work is on the order of 0.5 kcal/mol (for ozone). DBOC corrections are significant at the 0.1 kcal/mol level in hydride systems. . Based on the accumulated experience, a new computational thermochemistry protocol for first-and second-row main-group systems, to be known as W4 theory, is proposed. Our W4 atomization energies for a number of key species are in excellent agreement (better than 0.1 kcal/mol on average, 95% confidence intervals narrower than 1 kJ/mol) with the latest experimental data obtained from Active Thermochemical Tables. A simple {\em a priori} estimate for the importance of post-CCSD(T) correlation contributions (and hence a pessimistic estimate for the error in a W2-type calculation) is proposed.Comment: J. Chem. Phys., in press; electronic supporting information available at http://theochem.weizmann.ac.il/web/papers/w4.htm

Bounded Refinement Types

We present a notion of bounded quantification for refinement types and show how it expands the expressiveness of refinement typing by using it to develop typed combinators for: (1) relational algebra and safe database access, (2) Floyd-Hoare logic within a state transformer monad equipped with combinators for branching and looping, and (3) using the above to implement a refined IO monad that tracks capabilities and resource usage. This leap in expressiveness comes via a translation to "ghost" functions, which lets us retain the automated and decidable SMT based checking and inference that makes refinement typing effective in practice.Comment: 14 pages, International Conference on Functional Programming, ICFP 201

Effective statistical physics of Anosov systems

We present evidence indicating that Anosov systems can be endowed with a unique physically reasonable effective temperature. Results for the two paradigmatic Anosov systems (i.e., the cat map and the geodesic flow on a surface of constant negative curvature) are used to justify a proposal for extending Ruelle's thermodynamical formalism into a comprehensive theory of statistical physics for nonequilibrium steady states satisfying the Gallavotti-Cohen chaotic hypothesis.Comment: 38 pages, 17 figures. Substantially more details in sections 4 and 6; new and revised figures also added. Typos and minor errors (esp. in section 6) corrected along with minor notational changes. MATLAB code for calculations in section 16 also included as inline comment in TeX source now. The thrust of the paper is unaffecte

Hierarchical agent supervision

Agent supervision is a form of control/customization where a supervisor restricts the behavior of an agent to enforce certain requirements, while leaving the agent as much autonomy as possible. To facilitate supervision, it is often of interest to consider hierarchical models where a high level abstracts over low-level behavior details. We study hierarchical agent supervision in the context of the situation calculus and the ConGolog agent programming language, where we have a rich first-order representation of the agent state. We define the constraints that ensure that the controllability of in-dividual actions at the high level in fact captures the controllability of their implementation at the low level. On the basis of this, we show that we can obtain the maximally permissive supervisor by first considering only the high-level model and obtaining a high- level supervisor and then refining its actions locally, thus greatly simplifying the supervisor synthesis task

Requirements for software engineering languages

This paper analyzes the concepts of software construction embodied in the Draco system. The analysis relates specific mechanisms in Draco to particular software engineering (SE) principles and suggests future research needed to extend the approach. The purpose of the analysis is to help researchers understand Draco better and thus be able to direct in productive directions future research on this type of software engineering tool

Lattice refining loop quantum cosmology, anisotropic models and stability

A general class of loop quantizations for anisotropic models is introduced and discussed, which enhances loop quantum cosmology by relevant features seen in inhomogeneous situations. The main new effect is an underlying lattice which is being refined during dynamical changes of the volume. In general, this leads to a new feature of dynamical difference equations which may not have constant step-size, posing new mathematical problems. It is discussed how such models can be evaluated and what lattice refinements imply for semiclassical behavior. Two detailed examples illustrate that stability conditions can put strong constraints on suitable refinement models, even in the absence of a fundamental Hamiltonian which defines changes of the underlying lattice. Thus, a large class of consistency tests of loop quantum gravity becomes available. In this context, it will also be seen that quantum corrections due to inverse powers of metric components in a constraint are much larger than they appeared recently in more special treatments of isotropic, free scalar models where they were artificially suppressed.Comment: 24 page

Gradual Liquid Type Inference

Liquid typing provides a decidable refinement inference mechanism that is convenient but subject to two major issues: (1) inference is global and requires top-level annotations, making it unsuitable for inference of modular code components and prohibiting its applicability to library code, and (2) inference failure results in obscure error messages. These difficulties seriously hamper the migration of existing code to use refinements. This paper shows that gradual liquid type inference---a novel combination of liquid inference and gradual refinement types---addresses both issues. Gradual refinement types, which support imprecise predicates that are optimistically interpreted, can be used in argument positions to constrain liquid inference so that the global inference process e effectively infers modular specifications usable for library components. Dually, when gradual refinements appear as the result of inference, they signal an inconsistency in the use of static refinements. Because liquid refinements are drawn from a nite set of predicates, in gradual liquid type inference we can enumerate the safe concretizations of each imprecise refinement, i.e. the static refinements that justify why a program is gradually well-typed. This enumeration is useful for static liquid type error explanation, since the safe concretizations exhibit all the potential inconsistencies that lead to static type errors. We develop the theory of gradual liquid type inference and explore its pragmatics in the setting of Liquid Haskell.Comment: To appear at OOPSLA 201

Local Moment Instability of Os in Honeycomb Li2.15Os0.85O3.

Compounds with honeycomb structures occupied by strong spin orbit coupled (SOC) moments are considered to be candidate Kitaev quantum spin liquids. Here we present the first example of Os on a honeycomb structure, Li2.15(3)Os0.85(3)O3 (C2/c, a = 5.09 Å, b = 8.81 Å, c = 9.83 Å, β = 99.3°). Neutron diffraction shows large site disorder in the honeycomb layer and X-ray absorption spectroscopy indicates a valence state of Os (4.7 ± 0.2), consistent with the nominal concentration. We observe a transport band gap of Δ = 243 ± 23 meV, a large van Vleck susceptibility, and an effective moment of 0.85 μB, much lower than expected from 70% Os(+5). No evidence of long range order is found above 0.10 K but a spin glass-like peak in ac-susceptibility is observed at 0.5 K. The specific heat displays an impurity spin contribution in addition to a power law ∝T(0.63±0.06). Applied density functional theory (DFT) leads to a reduced moment, suggesting incipient itineracy of the valence electrons, and finding evidence that Li over stoichiometry leads to Os(4+)-Os(5+) mixed valence. This local picture is discussed in light of the site disorder and a possible underlying quantum spin liquid state