INLA or MCMC? A Tutorial and Comparative Evaluation for Spatial Prediction in log-Gaussian Cox Processes

We investigate two options for performing Bayesian inference on spatial log-Gaussian Cox processes assuming a spatially continuous latent field: Markov chain Monte Carlo (MCMC) and the integrated nested Laplace approximation (INLA). We first describe the device of approximating a spatially continuous Gaussian field by a Gaussian Markov random field on a discrete lattice, and present a simulation study showing that, with careful choice of parameter values, small neighbourhood sizes can give excellent approximations. We then introduce the spatial log-Gaussian Cox process and describe MCMC and INLA methods for spatial prediction within this model class. We report the results of a simulation study in which we compare MALA and the technique of approximating the continuous latent field by a discrete one, followed by approximate Bayesian inference via INLA over a selection of 18 simulated scenarios. The results question the notion that the latter technique is both significantly faster and more robust than MCMC in this setting; 100,000 iterations of the MALA algorithm running in 20 minutes on a desktop PC delivered greater predictive accuracy than the default \verb=INLA= strategy, which ran in 4 minutes and gave comparative performance to the full Laplace approximation which ran in 39 minutes.Comment: This replaces the previous version of the report. The new version includes results from an additional simulation study, and corrects an error in the implementation of the INLA-based method

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

Can ‘New Welfare’ Address Poverty through More and Better Jobs?

New welfare has been prominent in recent European social policy debates. It involves mobilising more people into paid work, improving human capital and ensuring fairer access to opportunities. This programme is attractive to business (more workers, better human capital and reduced social conflict to enhance productivity and profitability) and to citizens (more widely accessible job-opportunities with better rewards): a relatively low-cost approach to the difficulties governments face in maintaining support and meeting social goals as inequalities widen. The general move towards ‘new welfare’ gathered momentum during the past two decades, given extra impetus by the 2007-9 recession and subsequent stagnation. While employment rates rose during the prosperous years before the crisis, there was no commensurate reduction in poverty. Over the same period the share of economic growth returned to labour fell, labour markets were increasingly de-regulated and inequality increased. This raises the question of whether new welfare’s economic (higher employment, improved human capital) and social (better job quality and incomes) goals may come into conflict. This paper examines data for 17 European countries over the period 2001 to 2007. It shows that new welfare is much more successful at achieving higher employment than at reducing poverty, even during prosperity, and that the approach pays insufficient attention to structural factors, such as the falling wage share, and to institutional issues, such as labour market deregulation

Contributions of Repulsive and Attractive Interactions to Nematic Order

Both repulsive and attractive molecular interactions can be used to explain the onset of nematic order. The object of this paper is to combine these two nematogenic molecular interactions in a unified theory. This attempt is not unprecedented; what is perhaps new is the focus on the understanding of nematics in the high density limit. There, the orientational probability distribution is shown to exhibit a unique feature: it has compact support on configuration space. As attractive interactions are turned on, the behavior changes, and at a critical attractive interaction strength, thermotropic behavior of the Maier-Saupe type is attained.Comment: 14 pages, 4 figure

Density functional theory for dense nematics with steric interactions

The celebrated work of Onsager on hard particle systems, based on the truncated second order virial expansion, is valid at relatively low volume fractions for large aspect ratio particles. While it predicts the isotropic-nematic phase transition, it fails to provide a realistic equation of state in that the pressure remains finite for arbitrarily high densities. In this work, we derive a mean field density functional form of the Helmholtz free energy for nematics with hard core repulsion. In addition to predicting the isotropic-nematic transition, the model provides a more realistic equation of state. The energy landscape is much richer, and the orientational probability distribution function in the nematic phase possesses a unique feature: it vanishes on a nonzero measure set in orientational space

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

Adapting the International System of Units to the twenty-first century

We review the proposal of the International Committee for Weights and Measures (Comité International des Poids et Mesures, CIPM), currently being considered by the General Conference on Weights and Measures (Conférences Générales des Poids et Mesures, CGPM), to revise the International System of Units (Le Système International d’Unitès, SI). The proposal includes new definitions for four of the seven base units of the SI, and a new form of words to present the definitions of all the units. The objective of the proposed changes is to adopt definitions referenced to constants of nature, taken in the widest sense, so that the definitions may be based on what are believed to be true invariants. In particular, whereas in the current SI the kilogram, ampere, kelvin and mole are linked to exact numerical values of the mass of the international prototype of the kilogram, the magnetic constant (permeability of vacuum), the triple-point temperature of water and the molar mass of carbon-12, respectively, in the new SI these units are linked to exact numerical values of the Planck constant, the elementary charge, the Boltzmann constant and the Avogadro constant, respectively. The new wording used expresses the definitions in a simple and unambiguous manner without the need for the distinction between base and derived units. The importance of relations among the fundamental constants to the definitions, and the importance of establishing a mise en pratique for the realization of each definition, are also discussed