Ab Initio Calculations on the H_(2)+D_(2)=2HD Four‐Center Exchange Reaction. I. Elements of the Reaction Surface

We present the results of ab initio calculations on some interesting regions of the reaction surface for the four‐center exchange reaction H_(2)+D_(2)=2HD. These calculations, which use a minimum basis set of Slater orbitals, indicate that for all geometries appropriate to the transition state of the reaction, a barrier height of at least 148 kcal/mole is present. This is far greater than the energy required to produce free radicals and more than three times the experimental energy of activation, 42 kcal/mole. Considering the sources and magnitudes for errors due to correlation and basis set restrictions, we estimate the barrier height for this exchange reaction to be 132 ± 20 kcal/mole exclusive of zero‐point energies. In this paper we discuss the surface as determined by configuration interaction techniques. We find that the most favorable geometries for the exchange reactions are the square, rhombus, and kite configurations. However, all of these states are unstable with respect to H_(2) + 2H. In addition we find no evidence of collision complexes for any of the likely transition state geometries. In the following paper we will examine the G1 wavefunctions for this system in order to obtain an understanding of the factors responsible for the shape of the surface

The effect of a supplementary ('Gist-based') information leaflet on colorectal cancer knowledge and screening intention: a randomized controlled trial.

Guided by Fuzzy Trace Theory, this study examined the impact of a 'Gist-based' leaflet on colorectal cancer screening knowledge and intentions; and tested the interaction with participants' numerical ability. Adults aged 45-59 years from four UK general practices were randomly assigned to receive standard information ('The Facts', n = 2,216) versus standard information plus 'The Gist' leaflet (Gist + Facts, n = 2,236). Questionnaires were returned by 964/4,452 individuals (22 %). 82 % of respondents reported having read the information, but those with poor numeracy were less likely (74 vs. 88 %, p < .001). The 'Gist + Facts' group were more likely to reach the criterion for adequate knowledge (95 vs. 91 %; p < .01), but this was not moderated by numeracy. Most respondents (98 %) intended to participate in screening, with no group differences and no interaction with numeracy. The improved levels of knowledge and self-reported reading suggest 'The Gist' leaflet may increase engagement with colorectal cancer screening, but ceiling effects reduced the likelihood that screening intentions would be affected

Evaluation of appendicitis risk prediction models in adults with suspected appendicitis

Background Appendicitis is the most common general surgical emergency worldwide, but its diagnosis remains challenging. The aim of this study was to determine whether existing risk prediction models can reliably identify patients presenting to hospital in the UK with acute right iliac fossa (RIF) pain who are at low risk of appendicitis. Methods A systematic search was completed to identify all existing appendicitis risk prediction models. Models were validated using UK data from an international prospective cohort study that captured consecutive patients aged 16–45 years presenting to hospital with acute RIF in March to June 2017. The main outcome was best achievable model specificity (proportion of patients who did not have appendicitis correctly classified as low risk) whilst maintaining a failure rate below 5 per cent (proportion of patients identified as low risk who actually had appendicitis). Results Some 5345 patients across 154 UK hospitals were identified, of which two‐thirds (3613 of 5345, 67·6 per cent) were women. Women were more than twice as likely to undergo surgery with removal of a histologically normal appendix (272 of 964, 28·2 per cent) than men (120 of 993, 12·1 per cent) (relative risk 2·33, 95 per cent c.i. 1·92 to 2·84; P < 0·001). Of 15 validated risk prediction models, the Adult Appendicitis Score performed best (cut‐off score 8 or less, specificity 63·1 per cent, failure rate 3·7 per cent). The Appendicitis Inflammatory Response Score performed best for men (cut‐off score 2 or less, specificity 24·7 per cent, failure rate 2·4 per cent). Conclusion Women in the UK had a disproportionate risk of admission without surgical intervention and had high rates of normal appendicectomy. Risk prediction models to support shared decision‐making by identifying adults in the UK at low risk of appendicitis were identified

Exchange kinetic energy, contragradience, and chemical binding

The energy components of the G1 wavefunction for H_2 are carefully analyzed. It is found that the binding is dominated by the exchange part of the kinetic energy and that this term is dominant because of the contragradience of the orbitals in the bond region