Broken-Symmetry Unrestricted Hybrid Density Functional Calculations on Nickel Dimer and Nickel Hydride

In the present work we investigate the adequacy of broken-symmetry unrestricted density functional theory (DFT) for constructing the potential energy curve of nickel dimer and nickel hydride, as a model for larger bare and hydrogenated nickel cluster calculations. We use three hybrid functionals: the popular B3LYP, Becke's newest optimized functional Becke98, and the simple FSLYP functional (50% Hartree-Fock and 50% Slater exchange and LYP gradient-corrected correlation functional) with two basis sets: all-electron (AE) Wachters+f basis set and Stuttgart RSC effective core potential (ECP) and basis set. We find that, overall, the best agreement with experiment, comparable to that of the high-level CASPT2, is obtained with B3LYP/AE, closely followed by Becke98/AE and Becke98/ECP. FSLYP/AE and B3LYP/ECP give slightly worse agreement with experiment, and FSLYP/ECP is the only method among the ones we studied that gives an unaceptably large error, underestimating the dissociation energy of nickel dimer by 28%, and being in the largest disagreement with the experiment and the other theoretical predictions.Comment: 17 pages, 7 tables, 7 figures; submitted to J. Chem. Phys.; Revtex4/LaTeX2e. v2 (8/5/04): New (and better) ECP results, without charge density fitting (which was found to give large errors). Subtracted the relativistic corrections from all experimental value

Accurate Hartree-Fock energy of extended systems using large Gaussian basis sets

Calculating highly accurate thermochemical properties of condensed matter via wave function-based approaches (such as e.g. Hartree-Fock or hybrid functionals) has recently attracted much interest. We here present two strategies providing accurate Hartree-Fock energies for solid LiH in a large Gaussian basis set and applying periodic boundary conditions. The total energies were obtained using two different approaches, namely a supercell evaluation of Hartree-Fock exchange using a truncated Coulomb operator and an extrapolation toward the full-range Hartree-Fock limit of a Pad\'e fit to a series of short-range screened Hartree-Fock calculations. These two techniques agreed to significant precision. We also present the Hartree-Fock cohesive energy of LiH (converged to within sub-meV) at the experimental equilibrium volume as well as the Hartree-Fock equilibrium lattice constant and bulk modulus.Comment: 7.5 pages, 2 figures, submitted to Phys. Rev. B; v2: typos removed, References adde

Mott Transition of MnO under Pressure: Comparison of Correlated Band Theories

The electronic structure, magnetic moment, and volume collapse of MnO under pressure are obtained from four different correlated band theory methods; local density approximation + Hubbard U (LDA+U), pseudopotential self-interaction correction (pseudo-SIC), the hybrid functional (combined local exchange plus Hartree-Fock exchange), and the local spin density SIC (SIC-LSD) method. Each method treats correlation among the five Mn 3d orbitals (per spin), including their hybridization with three O $2p$ orbitals in the valence bands and their changes with pressure. The focus is on comparison of the methods for rocksalt MnO (neglecting the observed transition to the NiAs structure in the 90-100 GPa range). Each method predicts a first-order volume collapse, but with variation in the predicted volume and critical pressure. Accompanying the volume collapse is a moment collapse, which for all methods is from high-spin to low-spin (5/2 to 1/2), not to nonmagnetic as the simplest scenario would have. The specific manner in which the transition occurs varies considerably among the methods: pseudo-SIC and SIC-LSD give insulator-to-metal, while LDA+U gives insulator-to-insulator and the hybrid method gives an insulator-to-semimetal transition. Projected densities of states above and below the transition are presented for each of the methods and used to analyze the character of each transition. In some cases the rhombohedral symmetry of the antiferromagnetically ordered phase clearly influences the character of the transition.Comment: 14 pages, 9 figures. A 7 institute collaboration, Updated versio

LARS-like symptoms in the general population may suggest the significance of postoperative functional problems and emotional implications of rectal surgery

Background & Aim. Sphincter-saving rectal surgery is prone to cause changes in bowel function associated with Low Anterior Resection Syndrome (LARS). Our aim was to assess LARS-like symptoms within a population of 50-80-year old in order to understand the functional disturbances and emotional impact of LARS. Materials and methods: We used a questionnaire to evaluate LARS with the following categories of symptoms: flatulence control, anal incontinence, frequency, clustering and urgency of the stools, and the psycho-emotional impact created by the presence of these symptoms. We calculated the severity of LARS on 343 responders. Results. The average age of the responders (57.4% females) was 60 years. Overall, 48.1% of those questioned had no LARS-associated symptoms, while the rest presented either minor (39.9%) or major (12%) LARS-like symptomatology according to the assessment scale. Women have a higher relative risk (1.32) of having minor or major LARS. The frequency of stools did not correlate with the overall LARS score. The psycho-emotional impact was mostly influenced by the presence of incontinence (p=0.001) and urgency (p=0.05). Discussions. The study highlights the need to integrate the initial status of patients into the overall quantification of the effects of surgery on the quality of life. Age does not influence the prevalence of LARS, but symptoms seem more prevalent in women. The psycho-emotional impact is relevant to the general population, so explanations given during the informed consent and accurate description of potential consequences of surgical intervention increase compliance to ensure better post-operative control of the symptomatology. Conclusions. Deriving a normative LARS-like score may alter the interpretation and discussion of LARS scores for future rectal cancer patients, and it also provides a better understanding of the emotional impact of such symptoms on certain population subsets or cultural groups

LARS-like symptoms in the general population may suggest the significance of postoperative functional problems and emotional implications of rectal surgery

Background & Aim. Sphincter-saving rectal surgery is prone to cause changes in bowel function associated with Low Anterior Resection Syndrome (LARS). Our aim was to assess LARS-like symptoms within a population of 50-80-year old in order to understand the functional disturbances and emotional impact of LARS. Materials and methods: We used a questionnaire to evaluate LARS with the following categories of symptoms: flatulence control, anal incontinence, frequency, clustering and urgency of the stools, and the psycho-emotional impact created by the presence of these symptoms. We calculated the severity of LARS on 343 responders. Results. The average age of the responders (57.4% females) was 60 years. Overall, 48.1% of those questioned had no LARS-associated symptoms, while the rest presented either minor (39.9%) or major (12%) LARS-like symptomatology according to the assessment scale. Women have a higher relative risk (1.32) of having minor or major LARS. The frequency of stools did not correlate with the overall LARS score. The psycho-emotional impact was mostly influenced by the presence of incontinence (p=0.001) and urgency (p=0.05). Discussions. The study highlights the need to integrate the initial status of patients into the overall quantification of the effects of surgery on the quality of life. Age does not influence the prevalence of LARS, but symptoms seem more prevalent in women. The psycho-emotional impact is relevant to the general population, so explanations given during the informed consent and accurate description of potential consequences of surgical intervention increase compliance to ensure better post-operative control of the symptomatology. Conclusions. Deriving a normative LARS-like score may alter the interpretation and discussion of LARS scores for future rectal cancer patients, and it also provides a better understanding of the emotional impact of such symptoms on certain population subsets or cultural groups

An Electrochemical Oxygen Pump Model – A Tool for Sensor Optimization

AbstractElectrochemical oxygen pump sensors are increasingly important in a range of industrial sensing applications. However, their development has traditionally been based on inefficient empirical approaches. We have built a detailed finite-element model of an oxygen pump electrochemical sensor that is able to simulate the distribution of oxygen within sensor components under a range of conditions. This has been used to predict key performance parameters such as the steady state output current as a function of oxygen concentration, the startup characteristics and the transient response to a step change in oxygen concentration. The model is a powerful tool enabling multiple design concepts to be compared without the need for time consuming prototype sensor construction