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1.
《Mendeleev Communications》2022,32(6):777-779
The reactions of aryllithium reagents o-LiC6H4CH2NR2 with (MeO)2CO afford two new tris(aryl)carbinols bearing pendant-NR2 donor groups in the side chain [o-R NCH C H ] COH [R = Me, R + R = (CH) ]. These alcohols feature helical chirality due to differently inclined aromatic fragments and are presented in a crystalline cell as two M and P enantiomers. Carbinol (R = Me) readily reacts with (Me3SiCH2)3Sc(THF)2 to give a scandium bis(alkyl) complex [(o-C6H4CH2NMe2)3CO]Sc(CH2SiMe3)2 featuring rigid binding of the alkoxy anion through a κ1-O, κ2-N chelating coordination mode 相似文献
2.
Chemical bonding in representative astrophysically relevant neutral,cation, and anion HCnH chains
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Ioan Baldea 《中国物理 B》2022,31(12):123101-123101
Most existing studies assign a polyynic and cumulenic character of chemical bonding in carbon-based chains relying on values of the bond lengths. Building on our recent work, in this paper we add further evidence on the limitations of such an analysis and demonstrate the significant insight gained via natural bond analysis. Presently reported results include atomic charges, natural bond order and valence indices obtained from ab initio computations for representative members of the astrophysically relevant neutral and charged HC2k/2k+1H chain family. They unravel a series of counter-intuitive aspects and/or help naive intuition in properly understanding microscopic processes, e.g., electron removal from or electron attachment to a neutral chain. Demonstrating that the Wiberg indices adequately quantify the chemical bonding structure of the HC2k/2k+1H chains—while the often heavily advertised Mayer indices do not—represents an important message conveyed by the present study. 相似文献
3.
The annealing algorithm (Ref. 1) is modified to allow for noisy or imprecise measurements of the energy cost function. This is important when the energy cannot be measured exactly or when it is computationally expensive to do so. Under suitable conditions on the noise/imprecision, it is shown that the modified algorithm exhibits the same convergence in probability to the globally minimum energy states as the annealing algorithm (Ref. 2). Since the annealing algorithm will typically enter and exit the minimum energy states infinitely often with probability one, the minimum energy state visited by the annealing algorithm is usually tracked. The effect of using noisy or imprecise energy measurements on tracking the minimum energy state visited by the modified algorithms is examined.The research reported here has been supported under Contracts AFOSR-85-0227, DAAG-29-84-K-0005, and DAAL-03-86-K-0171 and a Purdue Research Initiation Grant. 相似文献
4.
This paper deals with mathematical human resource planning; more specifically, it suggests a new model for a manpower‐planning system. In general, we study a k‐classed hierarchical system where the workforce demand at each time period is satisfied through internal mobility and recruitment. The motivation for this work is based on various European Union incentives, which promote regional or local government assistance programs that could be exploited by firms not only for hiring and training newcomers, but also to improve the skills and knowledge of their existing personnel. In this respect, in our augmented mobility model we establish a new ‘training/standby’ class, which serves as a manpower inventory position for potential recruits. This class, which may very well be internal or external to the system, is incorporated into the framework of a non‐homogeneous Markov chain model. Furthermore, cost objectives are employed using the goal‐programming approach, under different operating assumptions, in order to minimize the operational cost in the presence of system's constraints and regulations. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
5.
The Boltzmann distribution used in the steady-state analysis of the simulated annealing algorithm gives rise to several scale invariant properties. Scale invariance is first presented in the context of parallel independent processors and then extended to an abstract form based on lumping states together to form new aggregate states. These lumped or aggregate states possess all of the mathematical characteristics, forms and relationships of states (solutions) in the original problem in both first and second moments. These scale invariance properties therefore permit new ways of relating objective function values, conditional expectation values, stationary probabilities, rates of change of stationary probabilities and conditional variances. Such properties therefore provide potential applications in analysis, statistical inference and optimization. Directions for future research that take advantage of scale invariance are also discussed. 相似文献
6.
We study the induced measure obtained from a 1-step Markov measure, supported by a topological Markov chain, after the mapping of the original alphabet onto another one. We give sufficient conditions for the induced measure to be a Gibbs measure (in the sense of Bowen) when the factor system is again a topological Markov chain. This amounts to constructing, when it does exist, the induced potential and proving its Hölder continuity. This is achieved through a matrix method. We provide examples and counterexamples to illustrate our results. 相似文献
7.
We show that using ionic liquids as reagents in conjunction with microwave heating it is possible to prepare primary alkyl halides from the corresponding alcohols rapidly. Using ionic liquids as solvents in conjunction with microwave heating it is possible to prepare aryl nitriles from the corresponding aryl bromides or iodides. The scope and limitations of using microwave-promotion as a tool in these reactions is discussed. 相似文献
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9.
Hidetaka Tobita 《Journal of Polymer Science.Polymer Physics》2004,42(14):2801-2812
The matrix formula developed in the context of heterochain theory, M?w = M?wp + WF ( I ? M )?1 S , was applied to describe the molecular weight development during free‐radical multicomponent polymerization. All of the required probabilistic parameters are expressed in terms of the kinetic‐rate constants and the various concentrations associated with them. In free‐radical polymerization, the number of heterochain types, N, needs to be extrapolated to infinity, and such extrapolation is conducted with only three different N values. This matrix formula can be used as a benchmark test if other approximate approaches can give reasonable estimates of the weight‐average molecular weights. The moment equations with the average pseudo‐kinetic‐rate constants for branching and crosslinking reactions may provide poor estimates when the copolymer composition drift during polymerization is very significant. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2801–2812, 2004 相似文献
10.