Multilevel and density functional electronic structure calculations of proton affinities and gas-phase basicities involved in biological phosphoryl transfer

Five multilevel model chemistries (CBS-QB3, G3B3, G3MP2B3, MCG3/3, and MC-QCISD/3) and seven hybrid density functional methods (PBE0, B1B95, B3LYP, MPW1KCIS, PBE1KCIS, and MPW1B95) have been applied to the calculation of gas-phase basicity and proton affinity values for a series of 17 molecules relevant to the study of biological phosphoryl transfer. In addition, W1 calculations were performed on a subset of molecules. The accuracy of the methods was assessed and the nature of systematic errors was explored, leading to the introduction of a set of effective bond enthalpy and entropy correction terms. The multicoefficient correlation methods (MCG3/3 and MC-QCISD), with inclusion of specific zero-point scale factors, slightly outperform the other multilevel methods tested (CBS-QB3, G3B3, and G3MP2B3), with significantly less computational cost, and in the case of MC-QCISD, slightly less severe scaling. Four density functional methods, PBE1KCIS, MPW1B95, PBE0, and B1B95 perform nearly as well as the multilevel methods. These results provide an important set of benchmarks relevant to biological phosphoryl transfer reactions.     

An integral kernel for weakly pseudoconvex domains

A new explicit construction of Cauchy–Fantappié kernels is introduced for an arbitrary weakly pseudoconvex domain with smooth boundary. While not holomorphic in the parameter, the new kernel reflects the complex geometry and the Levi form of the boundary. Some estimates are obtained for the corresponding integral operator, which provide evidence that this kernel and related constructions give useful new tools for complex analysis on this general class of domains.     

High transverse momentumη production in π− p, π+ p,andpp interactions at 280 GeV/c

The inclusive cross sections for η production by the interactions of 280 GeV/c momentum π^?, π⁺, and proton beams in hydrogen have been measured. The kinematical range covered is ?0.45<x _F <0.45, and 4.0<P _T <7.0 GeV/c for Feynmanx _F and transverse momentum respectively. The η to π⁰ cross section ratios are given for the three reactions. The ratio of π^? p to π⁺ p cross sections for η production in the above kinematic ranges is 1.22±0.08±0.11.     

Dynamic job assignment: A column generation approach with an application to surgery allocation

We consider the assignment of jobs to heterogeneous agents in a dynamic system with a rolling time horizon. An example is a hospital operating theatre where the jobs are surgeries and the agents are the surgeons. The paper is presented in the context of surgery allocation and the system is characterized as follows: Patients are grouped into categories and they arrive continually following a stochastic process. Patients in each group have specific time limits within which they need treatment and if it cannot be accommodated then the patients are outsourced. The service level is the percentage of patients in each group treated within the time limit. Surgery durations are stochastic and depend on the surgeon conducting the surgeries. Each surgeon has limited time available and expected overtime is penalized by a non-decreasing convex function. We develop a column generation approach for the assignment of already arrived patients and tentative future patients to surgeons on specific days. It balances the conflicting objectives of including as many arrived patients as possible within their time limits, maximizing the service level of future patients, and minimizing the expected overtime of surgeons. A computational study is conducted with the model embedded in a rolling time horizon frame. The study indicates that the assignment of patients based on our model increases system performance in terms of service level and reduced overtime compared to a First-Come-First-Served (FCFS) policy when the arrival rates of patients are medium to high compared to the capacity of the system.     

六方MoN的合成新路线

 在高温高压极端条件下利用CH₄Cl还原二氧化钼的方法合成了六方MoN。反应条件为：压力2 GPa,温度1 500 ℃,时间2 h。并利用XRD对合成产物进行了表征。经最小二乘法拟合后结果表明,该合成产物具有六方结构对称性,其晶格常数为a＝0.572 nm,c＝0.560 nm。经过对其衍射峰位和峰强进行拟合计算,并与实验结果进行比较, 结果表明 MoN 产物的空间群为P6₃/mmc,其中Mo原子位于2b (0, 0, 1/4)和6h (x, 2x, 1/4),x＝0.489。N原子位于2a (0, 0, 0)和6g (0.5, 0, 0)。所采用的方法具有反应条件易达到、反应时间短、反应产物单相性好等特点。