Correct quantum chemistry in a minimal basis from effective Hamiltonians

We describe how to create ab-initio effective Hamiltonians that qualitatively describe correct chemistry even when used with a minimal basis. The Hamiltonians are obtained by folding correlation down from a large parent basis into a small, or minimal, target basis, using the machinery of canonical transformations. We demonstrate the quality of these effective Hamiltonians to correctly capture a wide range of excited states in water, nitrogen, and ethylene, and to describe ground and excited state bond-breaking in nitrogen and the chromium dimer, all in small or minimal basis sets

Advances in Molecular Quantum Chemistry Contained in the Q-Chem 4 Program Package

A summary of the technical advances that are incorporated in the fourth major release of the Q-Chem quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and open-shell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Møller–Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Some specific chemical examples include calculations on the strongly correlated Cr2 dimer, exploring zeolite-catalysed ethane dehydrogenation, energy decomposition analysis of a charged ter-molecular complex arising from glycerol photoionisation, and natural transition orbitals for a Frenkel exciton state in a nine-unit model of a self-assembling nanotube

Syndromics: A Bioinformatics Approach for Neurotrauma Research

Substantial scientific progress has been made in the past 50 years in delineating many of the biological mechanisms involved in the primary and secondary injuries following trauma to the spinal cord and brain. These advances have highlighted numerous potential therapeutic approaches that may help restore function after injury. Despite these advances, bench-to-bedside translation has remained elusive. Translational testing of novel therapies requires standardized measures of function for comparison across different laboratories, paradigms, and species. Although numerous functional assessments have been developed in animal models, it remains unclear how to best integrate this information to describe the complete translational “syndrome” produced by neurotrauma. The present paper describes a multivariate statistical framework for integrating diverse neurotrauma data and reviews the few papers to date that have taken an information-intensive approach for basic neurotrauma research. We argue that these papers can be described as the seminal works of a new field that we call “syndromics”, which aim to apply informatics tools to disease models to characterize the full set of mechanistic inter-relationships from multi-scale data. In the future, centralized databases of raw neurotrauma data will enable better syndromic approaches and aid future translational research, leading to more efficient testing regimens and more clinically relevant findings

Petrographical and petrophysical properties of sandstones: statistical analysis as an approach to predict material behaviour and construction suitability

Most studies dealing with material properties of sandstones are based on a small data set. The present study utilizes petrographical and petrophysical data from 22 selected sandstones and ~300 sandstones from the literature to estimate/predict the material and weathering behaviour of characteristic sandstones. Composition and fabric properties were determined from detailed thin section analyses. Statistical methods applied consist of data distributions with whisker plots and linear regression with confidence regions for the petrophysical and weathering properties. To identify similarities between individual sandstones and to define groups of specific sandstone types, principal component and cluster analyses were applied. The results confirm an interaction between the composition, depositional environment, stratigraphic association and diagenesis, which leads to a particular material behaviour of sandstones. Three different types of pore radii distributions are observed, whereby each is derived from different pore space modifications during diagenesis and is associated with specific sandstone types: (1) bimodal with a maximum in capillary and micropores, (2) unimodal unequal with a maximum in smaller capillary pores and (3) unimodal equable with a maximum in larger capillary pores. Each distribution shows specific dependencies to water absorption, salt loading and hygric dilatation. The strength–porosity relationship shows dependence on the content of unstable lithic fragments, grain contact and type of pore radii distribution, cementation and degree of alteration. Sandstones showing a maximum of capillary pores and micropores (bimodal) exhibit a distinct hygric dilatation and low salt resistance. These sandstones are highly immature sublitharenites–litharenites, characterized by altered unstable rock fragments, which show pointed-elongated grain contacts, and some pseudomatrix. Quartz arenites and sublitharenites–litharenites which are strongly compacted and cemented, show unimodal unequal pore radii distributions, low porosity, high strength and a high salt resistance. The presence of swellable clay minerals in sublitharenites–litharenites leads to a medium to high hygric dilatation, whereas quartz arenites show little hygric dilatation. Sandstones with unimodal equal pore radii distribution mostly belong to weakly compacted and cemented mature quartz arenites. These are characterized by high water absorption and high porosity, low to medium strength and a low salt resistance. The data compiled in this study are used to create a sandstone quality catalogue. Since material properties are dependent on many different parameters of influence, the transition between different lithotypes is fluent

The behaviour of consolidated volcanic tuffs: weathering mechanisms under simulated laboratory conditions

Five volcanic tuffs ranging from dacitic tuffs of Hungary to rhyolite, phonolite and basaltic tuffs of Germany were consolidated under laboratory conditions. Prior to consolidation an anti-hygro, a hydrous consolidant, which reduces the swelling ability of clay minerals, was applied. The three consolidants, a silicic acid ester (SAE), an elastic silicic acid ester (eSAE) and an acrylate resin (PMMA) were applied on test specimens under vacuum. Petrographic characterisation (polarizing microscopy, XRD, SEM) provided data for fabric analyses and the mineral composition of the tuffs. Changes in fabric, effective porosity, density, tensile strength, ultrasonic wave velocity were evaluated after the treatment. Weathering simulation tests such as hygric dilatation and thermal dilatation aimed to prove the effectiveness of consolidation and the durability of consolidated tuff samples. More than 500 samples were analysed. The tests showed that SAE caused the highest increase in indirect tensile strength. The water absorption and the pore size distribution of the tuffs were modified by consolidation. The PMMA reduced the water absorption the most, whereas SAE modified it the least. All the tested consolidants increased the thermal dilatation of the tuffs. The changes in hygric dilatation were not uniform: for most tuffs SAE increased and PMMA decreased the hygric dilatation, although the clay-rich Habichtswald tuff showed the opposite trend. The changes in hygric and thermal behaviour of consolidated tuff require special care when specific consolidants are chosen. These products modify the physical properties of consolidated tuffs and change the behaviour of weathering