Molecular vibrations in a gradient extremal path

Summary The calculation of vibrational states using a gradient extremal path is discussed. Gradient extremal paths are defined by local criteria, which lead to stable solutions. This has certain advantages in comparison with a steepest-descent path, which is often difficult to determine accurately. For cases where a reaction path formalism is applicable, a path based on the gradient extremal concept gives results in close agreement with those obtained using traditional steepest-descent methods. We present algorithms for carrying out such calculations and also give some numerical results.     

Variational transition state theory without the minimum-energy path

In this paper we propose a method for carrying out variational transition state theory calculations without first obtaining a converged minimum-energy path (MEP). We illustrate the method in two ways, first of all by employing an unconverged MEP and secondly by using a dynamically optimized distinguished reaction path. Preliminary tests of the algorithm for the reactions OH+H₂→H₂O+H and C₂H₅→C₂H₄+H are very encouraging. Received: 22 January 1997 / Accepted: 11 March 1997     

Calculations of concentration dependences of chemical shifts for acrylamide in water—DMSO mixed solvent

The lattice model of associated solutions was used to calculate the concentration dependences of the chemical shifts of¹³C magnetic nuclei in the acrylamide molecule in water—DMSO solvent. Each pair of bonds between the acrylamide group containing a magnetic nucleus and the neighboring solvent molecule was assumed to additively contribute to the change in the chemical shift of the nucleus in question. The new approach affords the same accuracy in describing the experimental data at any ratios of the solution components. It was shown that the chemical shifts and the excess heat of mixing of the water—DMSO binary solution can be simultaneously described using the same set of energy parameters of the model. The model makes it possible to employ experimental data on chemical shifts for studying intermolecular interactions in solutions. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1983–1987, October, 1998.     

Simultaneous determination of radionuclides separable into natural decay series by use of time-interval analysis

A delayed coincidence method, time-interval analysis (TIA), has been applied to successive – decay events on the millisecond time-scale. Such decay events are part of the ²²⁰Rn²¹⁶Po (T_1/2 145 ms) (Th-series) and ²¹⁹Rn²¹⁵Po (T_1/2 1.78 ms) (Ac-series). By using TIA in addition to measurement of ²²⁶Ra (U-series) from -spectrometry by liquid scintillation counting (LSC), two natural decay series could be identified and separated. The TIA detection efficiency was improved by using the pulse-shape discrimination technique (PSD) to reject -pulses, by solvent extraction of Ra combined with simple chemical separation, and by purging the scintillation solution with dry N₂ gas. The U- and Th-series together with the Ac-series were determined, respectively, from alpha spectra and TIA carried out immediately after Ra-extraction. Using the ²²¹Fr²¹⁷At (T_1/2 32.3 ms) decay process as a tracer, overall yields were estimated from application of TIA to the ²²⁵Ra (Np-decay series) at the time of maximum growth. The present method has proven useful for simultaneous determination of three radioactive decay series in environmental samples.     

Fast Marching Method for Calculating Reactive Trajectories for Chemical Reactions

We present a method for computing classical Newtonian trajectories that minimize the path length or transit time from reactant to product. Our approach is based on a generalization of the fast-marching method, which allows us to construct the solution of the Hamilton-Jacobi equation for the action that optimizes the desired quantity. The resulting “reactive paths” can be interpreted as reaction coordinates but, unlike more conventional choices, they contain dynamical information about the chemical system of interest.     

Comparative bioanalytical study of3H-deramciclane in dog plasma, using a gas chromatography-nitrogen-selective detection (GC-NPD), a new GC-radiochemical detection (GC-RD) and a liquid scintillation method

Summary A new, highly sensitive and selective gas chromatography method, using radiochemical detection (GC-DR) was developed for the selective determination of³H-labelled deramciclane and its N-desmethyl metabolite in dog plasma. Inter-day accuracy and precision, as well as system suitability of the GC-RD method was investigated during the method validation. The calibration curve was proved to be linear (r=0.9986) in a wide concentration range (13–1000 ngeqv mL⁻¹) The lower limit of quantitation (LLOQ) was 13.7 ngeqv mL⁻¹, and the limit of the detection (LOD) was 1 ngeqv mL⁻¹. Using this new GC-RD method, plasma levels of³H-labelled deramciclane and its metabolite were determined in dogs, after the administration of a single 10 mg kg⁻¹ oral dose. Pharmacokinetic curves and the calculated pharmacokinetic parameters were compared to those obtained using a previously elaborated gas chromatography-nitrogen selective detection method (GC-NPD) and to those obtained by measuring the plasma level of total radioactivity (liquid scintillation counting, LSC). Pharmacokinetic curves and the calculated pharmacokinetic parameters obtained with the two different gas chromatography detection methods (NPD and RD) showed good correlation. Comparison of these results to those acquired by total radioactivity measurement demonstrated that deramciclane was intensively metabolised. Moreover, the biological half-life (t ₁ ^2/β ) of the unknown metabolites proved to be more than a magnitude longer than the half-life of the parent compound or that of N-desmethyl metabolite. Presented at: Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 3–5, 1997.     

Traveling waves for a four-compartment lattice epidemic system with exposed class and standard incidence

This paper is considering the problem of traveling wave solutions (TWS) for a susceptible-exposed-infectious-recovered (SEIR) epidemic model with discrete diffusion. The threshold condition for the existence and nonexistence of TWS is obtained. More specifically, such kind of solutions are governed by the threshold number ?₀. We can find a critical wave speed c^? if ?₀ > 1, by employing the Schauder's fixed point theorem, limiting argument and two-sided Laplace transform, we confirm that there exists TWS for c > c^?, while there exists no TWS for c < c^?. We also obtain the nonexistence of TWS for ?₀ ≤ 1. At last, we give some biological explanations from the epidemiological perspective.     

N叉树上的离散时间量子随机行走

通过离散时间量子随机行走的框架,我们研究了在N叉树上的离散时间量子随机行走,该框架不需要硬币空间,仅仅只需要选择一个除了酉性再无其它限制的演化算子,并且包含了使用再生结构的轨道枚举和z变换.作为结果,我们在封闭形式中计算了在根处的振幅的生成函数.     

基于网格化管理视角下灾后应急物流决策模型与算法研究

灾害发生后,应急资源的需求预测与应急配送中心的合理选址是实现高效救援的关键。本文通过在网格化管理视角下的信息更新将应急救援过程划分为多个阶段,在开展救援的过程中实现救援信息收集和救援预测的同步开展,建立一种多阶段带时间约束的应急救援物资配送响应-时效性的选址模型。借助遗传算法(NSGA-II),实现了基于编码结构独立、路径相互关联基础上的多目标规划求解。本研究的决策模型及算法有着较好的搜索与寻优能力,对实际救援开展具有指导意义。