A definitive heat of vaporization of silicon through benchmark ab initio calculations on SiF_4

In order to resolve a significant uncertainty in the heat of vaporization of silicon -- a fundamental parameter in gas-phase thermochemistry -- $\Delta H^\circ_{f,0}$[Si(g)] has been determined from a thermochemical cycle involving the precisely known experimental heats of formation of SiF_4(g) and F(g) and a benchmark calculation of the total atomization energy (TAE_0) of SiF_4 using coupled-cluster methods. Basis sets up to $[8s7p6d4f2g1h]$ on Si and $[7s6p5d4f3g2h]$ on F have been employed, and extrapolations for residual basis set incompleteness applied. The contributions of inner-shell correlation (-0.08 kcal/mol), scalar relativistic effects (-1.88 kcal/mol), atomic spin-orbit splitting (-1.97 kcal/mol), and anharmonicity in the zero-point energy (+0.04 kcal/mol) have all been explicitly accounted for. Our benchmark TAE_0=565.89 \pm 0.22 kcal/mol leads to $\Delta H^\circ_{f,0}$[Si(g)]=107.15 \pm 0.38 kcal/mol ($\Delta H^\circ_{f,298}$[Si(g)]=108.19 \pm 0.38 kcal/mol): between the JANAF/CODATA value of 106.5 \pm 1.9 kcal/mol and the revised value proposed by Grev and Schaefer [J. Chem. Phys. 97, 8389 (1992}], 108.1 \pm 0.5 kcal/mol. The revision will be relevant for future computational studies on heats of formation of silicon compounds.Comment: J. Phys. Chem. A, submitted Feb 1, 199

A Design Strategy for Deadlock-Free Concurrent Systems

When building concurrent systems, it would be useful to have a collection of reusable processes to perform standard tasks. However, without knowing certain details of the inner workings of these components, one can never be sure that they will not cause deadlock when connected to some particular network. Here we describe a hierarchical method for designing complex networks of communicating processeswhich are deadlock-free.We use this to define a safe and simple method for specifying the communication interface to third party software components. This work is presented using the CSP model of concurrency and the occam2.1 programming language

On the properties of the transition matrix in bouncing cosmologies

We elaborate further on the evolution properties of cosmological fluctuations through a bounce. We show this evolution to be describable either by ``transmission'' and ``reflection'' coefficients or by an effective unitary S-matrix. We also show that they behave in a time reversal invariant way. Therefore, earlier results are now interpreted in a different perspective and put on a firmer basis.Comment: 4 pages, 1 figure, to appear in PR

Strong, Bold, and Kind: Self-Control and Cooperation in Social Dilemmas

We develop a model relating self-control, risk preferences and conflict identification to cooperation patterns in social dilemmas. We subject our model to data from an experimental public goods game and a risk experiment, and we measure conflict identification and self-control. As predicted, we find a robust association between self-control and higher levels of cooperation, and the association is weaker for more risk-averse individuals. Free riders differ from other contributor types only in their tendency not to have identified a self-control conflict in the first place. Our model accounts for the data at least as well as do other models

Do Childhood Vaccines Have Non-Specific Effects on Mortality

A recent article by Kristensen et al. suggested that measles vaccine and bacille Calmette–Guérin (BCG) vaccine might\ud reduce mortality beyond what is expected simply from protection against measles and tuberculosis. Previous reviews of the potential effects of childhood vaccines on mortality have not considered methodological features of reviewed studies. Methodological considerations play an especially important role in observational assessments, in which selection factors for vaccination may be difficult to ascertain. We reviewed 782 English language articles on vaccines and childhood mortality and found only a few whose design met the criteria for methodological rigor. The data reviewed suggest that measles vaccine delivers its promised reduction in mortality, but there is insufficient evidence to suggest a mortality benefit above that caused by its effect on measles disease and its sequelae. Our review of the available data in the literature reinforces how difficult answering these considerations has been and how important study design will be in determining the effect of specific vaccines on all-cause mortality.\u

An ab initio study of the C3(+) cation using multireference methods

The energy difference between the linear 2 sigma(sup +, sub u) and cyclic 2B(sub 2) structures of C3(+) has been investigated using large (5s3p2d1f) basis sets and multireference electron correlation treatments, including complete active space self consistent fields (CASSCF), multireference configuration interaction (MRCI), and averaged coupled-pair functional (ACPF) methods, as well as the single-reference quadratic configuration interaction (QCISD(T)) method. Our best estimate, including a correction for basis set incompleteness, is that the linear form lies above the cyclic from by 5.2(+1.5 to -1.0) kcal/mol. The 2 sigma(sup +, sub u) state is probably not a transition state, but a local minimum. Reliable computation of the cyclic/linear energy difference in C3(+) is extremely demanding of the electron correlation treatment used: of the single-reference methods previously considered, CCSD(T) and QCISD(T) perform best. The MRCI + Q(0.01)/(4s2p1d) energy separation of 1.68 kcal/mol should provide a comparison standard for other electron correlation methods applied to this system

On the "Causality Argument" in Bouncing Cosmologies

We exhibit a situation in which cosmological perturbations of astrophysical relevance propagating through a bounce are affected in a scale-dependent way. Involving only the evolution of a scalar field in a closed universe described by general relativity, the model is consistent with causality. Such a specific counter-example leads to the conclusion that imposing causality is not sufficient to determine the spectrum of perturbations after a bounce provided it is known before. We discuss consequences of this result for string motivated scenarios.Comment: 4 pages, 1 figure, ReVTeX, to appear in Phys. Rev. Let