Search

Accurate prediction of fundamental band gaps of crystalline solid-state systems entirely within density functional theory is a long-standing challenge. Here, we present a simple and inexpensive method that achieves this by means of nonempirical optimal tuning of the parameters of a screened range-separated hybrid functional. The tuning involves the enforcement of an ansatz that generalizes the ionization potential theorem to the removal of an electron from an occupied state described by a localized Wannier function in a modestly sized supercell calculation. The method is benchmarked against experiment for a set of systems ranging from narrow band-gap semiconductors to large band-gap insulators, spanning a range of fundamental band gaps from 0.2 to 14.2 electronvolts (eV), and is found to yield quantitative accuracy across the board, with a mean absolute error of ∼0.1 eV and a maximal error of ∼0.2 eV., Competing Interests: The authors declare no competing interest.

Electrochemical oxygen gas sensors are widely used for monitoring the state of inertisation of flammable atmospheres and to warn of asphyxiation risks. It is well established but not widely known by users of such oxygen sensors that the response of the sensor is affected by the nature of the diluent gas responsible for the decrease in ambient oxygen concentration. The present work investigates the response of electrochemical sensors, with either acid or alkaline electrolytes, to gas mixtures comprising air with enhanced levels of nitrogen, carbon dioxide, argon or helium. The measurements indicate that both types of sensors over-read the oxygen concentrations when atmospheres contain high levels of helium. Sensors with alkaline electrolytes are also shown to underestimate the severity of the hazard in atmospheres containing high levels of carbon dioxide. This deviation is greater for alkaline electrolyte sensors compared to acid electrolyte sensors. A Computational Fluid Dynamics (CFD) model is developed to predict the response of an alkaline electrolyte, electrochemical gas sensor. Differences between predicted and measured sensor responses are less than 10% in relative terms for nearly all of the gas mixtures tested, and in many cases less than 5%. Extending the model to simulate responses of sensors with acid electrolytes would be straightforward., (Crown Copyright © 2010. Published by Elsevier B.V. All rights reserved.)

Ventilation is frequently used as a means for preventing the build up of flammable or toxic gases in enclosed spaces. The effectiveness of the ventilation often has to be considered as part of a safety case or risk assessment. In this paper methods for assessing ventilation effectiveness for hazardous area classification are examined. The analysis uses data produced from Computational Fluid Dynamics (CFD) simulations of low-pressure jet releases of flammable gas in a ventilated enclosure. The CFD model is validated against experimental measurements of gas releases in a ventilation-controlled test chamber. Good agreement is found between the model predictions and the experimental data. Analysis of the CFD results shows that the flammable gas cloud volume resulting from a leak is largely dependent on the mass release rate of flammable gas and the ventilation rate of the enclosure. The effectiveness of the ventilation for preventing the build up of flammable gas can therefore be assessed by considering the average gas concentration at the enclosure outlet(s). It is found that the ventilation rate of the enclosure provides a more useful measure of ventilation effectiveness than considering the enclosure air change rate., (Crown Copyright © 2010. Published by Elsevier B.V. All rights reserved.)