Exploring non-adiabaticity to CO reduction reaction through ab initio molecular dynamics simulation

Non-adiabatic chemical reaction refers to the electronic excitation during reactions. This effect cannot be modeled by the ground-state Born-Oppenheimer molecular dynamics (BO-MD), where the electronic structure is at the ground state for every step of ions' movement. Although the non-adiabatic effect has been explored extensively in gas phase reactions, its role in electrochemical reactions, such as water splitting and CO2 reduction, in electrolyte has been rarely explored. On the other hand, electrochemical reactions usually involve electron transport; thus, a non-adiabatic process can naturally play a significant role. In this work, using one-step CO2 reduction as an example, we investigated the role of the non-adiabatic effect in the reaction. The reaction barriers were computed by adiabatic BO-MD and non-adiabatic real-time time dependent density functional theory (rt-TDDFT). We found that by including the non-adiabatic effect, rt-TDDFT could increase the reaction barrier up to 6% compared to the BO-MD calculated barrier when the solvent model is used to represent water. Simulations were carried out using explicit water molecules around the reaction site under different overpotentials, and similar non-adiabatic effects were found

Wannier–Koopmans method calculations for transition metal oxide band gaps

The widely used density functional theory (DFT) has a major drawback of underestimating the band gaps of materials. Wannier–Koopmans method (WKM) was recently developed for band gap calculations with accuracy on a par with more complicated methods. WKM has been tested for main group covalent semiconductors, alkali halides, 2D materials, and organic crystals. Here we apply the WKM to another interesting type of material system: the transition metal (TM) oxides. TM oxides can be classified as either with d0 or d10 closed shell occupancy or partially occupied open shell configuration, and the latter is known to be strongly correlated Mott insulators. We found that, while WKM provides adequate band gaps for the d0 and d10 TM oxides, it fails to provide correct band gaps for the group with partially occupied d states. This issue is also found in other mean-field approaches like the GW calculations. We believe that the problem comes from a strong interaction between the occupied and unoccupied d-state Wannier functions in a partially occupied d-state system. We also found that, for pseudopotential calculations including deep core levels, it is necessary to remove the electron densities of these deep core levels in the Hartree and exchange–correlation energy functional when calculating the WKM correction parameters for the d-state Wannier functions

The accurate staging of ovarian cancer using 3T magnetic resonance imaging - a realistic option

Objectives: The aim of the study was to determine whether staging primary ovarian cancer using 3.0 Tesla (3T) magnetic resonance imaging (MRI) is comparable to surgical staging of the disease. Design: A retrospective study consisting of a search of the pathology database to identify women with ovarian pathology from May 2004 to January 2007. Setting: All women treated for suspected ovarian cancer in our cancer centre region. Sample: All women suspected of ovarian pathology who underwent 3T MRI prior to primary surgical intervention between May 2004 and January 2007. Methods: All women found to have ovarian pathology, both benign and malignant, were then cross checked with the magnetic resonance (MR) database to identify those who had undergone 3T MRI prior to surgery. The resulting group of women underwent comparison of the MR, surgical and histopathological findings for each individual including diagnosis of benign or malignant disease and International Federation of Gynecology and Obstetrics (FIGO) staging where appropriate. Main outcome measures: Comparisons were made between the staging accuracy of 3T MRI and surgical staging compared with histopathological findings and FIGO stage using weighted kappa. Sensitivity, specificity and accuracy were calculated for diagnosing malignant ovarian disease with 3T MRI. Results: A total of 191 women identified as having ovarian pathology underwent imaging with 3T MR and primary surgical intervention. In 19 of these women, the ovarian disease was an incidental finding. The group for which staging methods were compared consisted of 77 women of primary ovarian malignancy (20 of whom had borderline tumours). 3T MRI was able to detect ovarian malignancy with a sensitivity of 92% and a specificity of 76%. The overall accuracy in detecting malignancy with 3T MRI was 84%, with a positive predictive value of 80% and negative predictive value of 90%. Statistical analysis of the two methods of staging using weighted kappa, gave a K value of 0.926 (SE ±0.121) for surgical staging and 0.866 (SE ±0.119) for MR staging. A further analysis of the staging data for ovarian cancers alone, excluding borderline tumours resulted in a K value of 0.931 (SE ±0.136) for histopathological staging versus MR staging and 0.958 (±0.140) for histopathological stage versus surgical staging. Conclusion: Our study has shown that MRI can achieve staging of ovarian cancer comparable with the accuracy seen with surgical staging. No previous studies comparing different modalities have used the higher field strength 3T MRI. In addition, all other studies comparing radiological assessment of ovarian cancer have grouped the stages into I, II, III and IV rather than the more clinically appropriate a, b and c subgroups. © 2008 The Authors

Archaeological building investigation and evaluation : City Tower, Todd Street, Manchester

In July 2016, Salford Archaeology was commissioned by Unique Boutique Hotels (Manchester) Ltd to undertake an historic building investigation of the former Cathedral School on Todd Street, Manchester (centred on SJ 8406 9886). Following the demolition of the building in November 2016, Bowmer & Kirkland Ltd commissioned Salford Archaeology to carry out an archaeological evaluation on the land. Both elements of the project were required as part of a redevelopment scheme. The historic building investigation was commensurate with a Level I-type survey, and the evaluation comprised the excavation of a single trench, which aimed to establish the presence or absence of buried archaeological remains within the proposed development area. An archaeological desk-based assessment compiled in 2010 demonstrated that the study area had the potential for the survival of remains relating to 18th- and 19th-century buildings, including housing, public houses and a series of schools. The site’s proximity to the original medieval core of Manchester also raised the possibility for earlier medieval remains being present in uncellared areas of the site, particularly within a former central courtyard. The historic building investigation concluded that the remnants of the former Cathedral School had been subject to considerable remodelling and alterations during the later 19th and 20th centuries, particularly in the basement and ground floor, with a resultant loss of historic fabric. The investigation has enabled an appropriate record of the building to be completed prior to its demolition. The evaluation trench excavated across the study area revealed that basements had removed all remains at the south-east and north-west ends of the trench. Natural gravels were observed between these basements, but did not contain any features of archaeological significance. The natural gravels were tested by excavating a sondage to 4.2m, and were shown to be consistent throughout, becoming much more indurated at depth. The results obtained from the evaluation trenches have indicated that no remains of archaeological significance survive within the study area, and that no further archaeological work in advance of development is merited

DEFECT PHENOMENA IN SUPERCONDUCTING OXIDES AND ANALOGOUS CERAMIC OXIDES

In this review we discuss defect phenomena in superconducting oxides. We survey those aspects of oxide superconductors which relate them most closely to conventional ceramic oxides, concentrating on processes and behaviour related to defects. We also identify areas of difference between two types of oxide.Theoretical modelling of conventional oxides has been extremely effective, and we emphasize that some of these modelling tools can be exploited for the superconducting oxides too. In particular, we stress those methods and ideas that provide a framework for understanding behaviour, those that provide a datasbase of good quantitative experiments and those that provide an established and tested approach to quantitative modelling as a guide to prediction, optimization and extrapolation.Much progress has been made in both theory and experiment, but some problems do remain and these have not been omitted from our discussions. There is potential to exploit past work on defects in oxides, so as to control defect processes and microstructure and hence to enhance performance

On staying grounded and avoiding Quixotic dead ends

The 15 articles in this special issue on The Representation of Concepts illustrate the rich variety of theoretical positions and supporting research that characterize the area. Although much agreement exists among contributors, much disagreement exists as well, especially about the roles of grounding and abstraction in conceptual processing. I first review theoretical approaches raised in these articles that I believe are Quixotic dead ends, namely, approaches that are principled and inspired but likely to fail. In the process, I review various theories of amodal symbols, their distortions of grounded theories, and fallacies in the evidence used to support them. Incorporating further contributions across articles, I then sketch a theoretical approach that I believe is likely to be successful, which includes grounding, abstraction, flexibility, explaining classic conceptual phenomena, and making contact with real-world situations. This account further proposes that (1) a key element of grounding is neural reuse, (2) abstraction takes the forms of multimodal compression, distilled abstraction, and distributed linguistic representation (but not amodal symbols), and (3) flexible context-dependent representations are a hallmark of conceptual processing

Tetranychid mites of Tasmania

Formerly only four species of the family Tetranychidae had been recorded from Tasmania. Collections of mites from both introduced and native plants have revealed that the family is represented by ten genera of which two are new. Fifteen species, five being new, are now recorded from the State. The following new genera and species are described:- New genera-Synonychus, Tylonychus. New species-Synonychus eucalypti, Eutetranychus acaciae, Tylonychus tasmaniensis, Eotetranychus hudsoni and Tetranychus rhagodiae. In addition the male of Schizonobia sycophanta Wom. is described for the first time

Finite-size effects in lead scandium tantalate relaxor thin films

Large electromechanical effects in relaxor ferroelectrics are generally attributed to the collective response of an ensemble of correlated, nanometer-sized polar structures induced by chemical and charge disorder. Here, we study finite-size effects on such polar order (i.e., how it evolves when sample dimensions approach the polarization correlation length) in 7-70-nm-thick films of the relaxor ferroelectric PbSc0.5Ta0.5O3. Temperature-dependent polarization studies reveal a linear suppression of the polarization and nonlinearity associated with relaxor order as the film thickness decreases to ≈30 nm. Below this thickness, however, the suppression rapidly accelerates, and polarization is completely absent by film thicknesses of ≈7 nm, despite the continued observation of a broad peak in dielectric permittivity and frequency dispersion. Diffuse-scattering measurements reveal the diffuse-scattering symmetry, and analysis suggests the films have a polarization correlation length of ≈23 nm. Taken together, it is apparent that reduction of sample size and the resulting distribution of polar structures drive suppression and eventual quenching of the electrical response of relaxors, which may be attributed to increasing dipole-dipole and dipole-interface interactions

Colour analysis of degraded parchment

Multispectral imaging was employed to collect data on the degradation of an 18th century parchment by a series of physical and chemical treatments. Each sample was photographed before and after treatment by a monochrome digital camera with 21 narrow-band filters. A template-matching technique was used to detect the circular holes in each sample and a four-point projective transform to register the 21 images. Colour accuracy was verified by comparison of reconstructed spectra with measurements by spectrophotometer