Exploring Alternate Methods for the Calculation of High-Level Vibrational Corrections of NMR Spin-Spin Coupling Constants.

Traditional nuclear magnetic resonance (NMR) calculations typically treat systems with a Born-Oppenheimer-derived electronic wave function that is solved for a fixed nuclear geometry. One can numerically account for this neglected nuclear motion by averaging over property values for all nuclear geometries with a vibrational wave function and adding this expectation value as a correction to an equilibrium geometry property value. Presented are benchmark coupled-cluster singles and doubles (CCSD) vibrational corrections to spin-spin coupling constants (SSCCs) computed at the level of vibrational second-order perturbation theory (VPT2) using the vibrational averaging driver of the CFOUR program. As CCSD calculations of vibrational corrections are very costly, cheaper electronic structure methods are explored via a newly developed Python vibrational averaging program within the Dalton Project. Namely, results obtained with the second-order polarization propagator approximation (SOPPA) and density functional theory (DFT) with the B3LYP and PBE0 exchange-correlation functionals are compared to the benchmark CCSD//CCSD(T) and experimental values. CCSD//CCSD(T) corrections are also combined with literature CC3 equilibrium geometry values to form the highest-order vibrationally corrected values available (i.e., CC3//CCSD(T) + CCSD//CCSD(T)). CCSD//CCSD(T) statistics showed favorable statistics in comparison to experimental values, albeit at an unfavorably high computational cost. A cheaper CCSD//CCSD(T) + B3LYP method showed quite similar mean absolute deviation (MAD) values as CCSD//CCSD(T), concluding that CCSD//CCSD(T) + B3LYP is optimal in terms of cost and accuracy. With reference to experimental values, a vibrational correction was not worth the cost for all of the other methods tested. Finally, deviation statistics showed that CC3//CCSD(T) + CCSD//CCSD(T) vibrational-corrected equilibrium values deteriorated in comparison to CCSD//CCSD(T) attributed to the use of a smaller basis set or lack of solvation effects for the CC3 equilibrium calculations.

A Combined Experimental and Theoretical Study of ESR Hyperfine Coupling Constants for N,N,N',N'-Tetrasubstituted p-Phenylenediamine Radical Cations.

A test set of N,N,N',N'-tetrasubstituted p-phenylenediamines are experimentally explored using ESR (electron spin resonance) spectroscopy and analysed from a computational standpoint thereafter. This computational study aims to further aid structural characterisation by comparing experimental ESR hyperfine coupling constants (hfccs) with computed values calculated using ESR-optimised "J-style" basis sets (6-31G(d,p)-J, 6-31G(d,p)-J, 6-311++G(d,p)-J, pcJ-1, pcJ-2 and cc-pVTZ-J) and hybrid-DFT functionals (B3LYP, PBE0, TPSSh, ωB97XD) as well as MP2. PBE0/6-31g(d,p)-J with a polarised continuum solvation model (PCM) correlated best with the experiment, giving an R2 value of 0.8926. A total of 98% of couplings were deemed satisfactory, with five couplings observed as outlier results, thus degrading correlation values significantly. A higher-level electronic structure method, namely MP2, was sought to improve outlier couplings, but only a minority of couples showed improvement, whilst the remaining majority of couplings were negatively degraded.

Improved Perinatal Mortality in Twins--Changing Practice and Technologies.

OBJECTIVE: We set out to examine rates of perinatal mortality in twin pregnancies over a 17-year study period. Changes in mode of delivery were also examined as well as causes of death in twin mortalities. STUDY DESIGN: This retrospective cohort study was performed at three large tertiary referral centers from 1996 to 2012. It included all normally formed twin infants with a birth weight more than 500 g. All cases of perinatal mortality in twin pregnancies (infants more than 500 g who suffered an intrauterine or early neonatal (≤ 7 days of age) death were recorded. The changing rate of cesarean delivery as well as varying causes of death in twins over the course of the study were also examined. RESULTS: During the study period, there were 395,830 pregnancies across the three institutions, this included 6,727 twin gestations. The perinatal mortality rate was 21.5/1,000 twin infants. The perinatal mortality rate in twins decreased over the study period (p = 0.0006; R (2) = 0.55; slope = -1.2). Rates of cesarean delivery in twin gestations were found to have increased over the course of the study (p < 0.0001; R (2) = 0.84; slope = 1.7). There were 288 intrauterine and early neonatal deaths in twin infants, 50% (147/288) occurred in twins born extremely premature (< 26 weeks). Prematurity was the leading cause of mortality in twins, followed by twin-to-twin transfusion syndrome (TTTS). TTTS was found to have a decreasing contribution to perinatal mortality during the study (p = 0.008; R (2) = 0.38; slope = -1.5). CONCLUSION: The perinatal mortality rate in twins improved during the study. The rate of cesarean delivery increased by 1.7% for each year of the study, culminating in a cesarean delivery rate of 62% in 2012. TTTS made a decreasing contribution to the mortality rate in twins during the study.

Oxytocin bolus versus oxytocin bolus and infusion for control of blood loss at elective caesarean section: double blind, placebo controlled, randomised trial.

OBJECTIVES: To determine the effects of adding an oxytocin infusion to bolus oxytocin on blood loss at elective caesarean section. DESIGN: Double blind, placebo controlled, randomised trial, conducted from February 2008 to June 2010. SETTING: Five maternity hospitals in the Republic of Ireland. PARTICIPANTS: 2069 women booked for elective caesarean section at term with a singleton pregnancy. We excluded women with placenta praevia, thrombocytopenia, coagulopathies, previous major obstetric haemorrhage (>1000 mL), or known fibroids; women receiving anticoagulant treatment; those who did not understand English; and those who were younger than 18 years. INTERVENTION: Intervention group: intravenous slow 5 IU oxytocin bolus over 1 minute and additional 40 IU oxytocin infusion in 500 mL of 0.9% saline solution over 4 hours (bolus and infusion). Placebo group: 5 IU oxytocin bolus over 1 minute and 500 mL of 0.9% saline solution over 4 hours (placebo infusion) (bolus only). Main outcomes Major obstetric haemorrhage (blood loss >1000 mL) and need for an additional uterotonic agent. RESULTS: We found no difference in the occurrence of major obstetric haemorrhage between the groups (bolus and infusion 15.7% (158/1007) v bolus only 16.0% (159/994), adjusted odds ratio 0.98, 95% confidence intervals 0.77 to 1.25, P=0.86). The need for an additional uterotonic agent in the bolus and infusion group was lower than that in the bolus only group (12.2% (126/1033) v 18.4% (189/1025), 0.61, 0.48 to 0.78, P<0.001). Women were less likely to have a major obstetric haemorrhage in the bolus and infusion group than in the bolus only group if the obstetrician was junior rather than senior (0.57, 0.35 to 0.92, P=0.02). CONCLUSION: The addition of an oxytocin infusion after caesarean delivery reduces the need for additional uterotonic agents but does not affect the overall occurrence of major obstetric haemorrhage. Trial Registration Current Controlled Trials ISRCTN17813715.