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1.
2.
The structure and rotational barrier for the mesityl-silicon bond of 2,2-dimesityl-1,1,1,3,3,3-hexamethyltrisilane have been investigated by 1H- and 13C-variable temperature nuclear magnetic resonance (NMR) as well as by density functional theory structural calculations. The calculations show that the lowest energy structure has C2 symmetry with nonequivalent ortho methyl groups, consistent with the crystal structure and solution NMR. The nonequivalent ortho methyl groups exchange through a Cs transition state with a calculated relative free energy of 11.0 kcal mol−1. The barrier for this rotation found by dynamic NMR is 13.4 ± 0.2 kcal mol−1 at 298 K. 相似文献
3.
Dr. Liat Avram Dr. Václav Havel Ronit Shusterman-Krush Dr. Mark A. Iron Dr. Moritz Zaiss Prof. Vladimír Šindelář Dr. Amnon Bar-Shir 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(7):1687-1690
The accumulated knowledge regarding molecular architectures is based on established, reliable, and accessible analytical tools that provide robust structural and functional information on assemblies. However, both the dynamicity and low population of noncovalently interacting moieties within studied molecular systems limit the efficiency and accuracy of traditional methods. Herein, the use of a saturation transfer-based NMR approach to study the dynamic binding characteristics of an anion to a series of synthetic receptors derived from bambusuril macrocycles is demonstrated. The exchange rates of BF4− are mediated by the side chains on the receptor (100 s−1<kex<5000 s−1), which play a critical role in receptor-anion binding dynamics. The signal amplification obtained with this approach allows for the identification of different types of intermolecular interactions between the receptor and the anion, something that could not have been detected by techniques hitherto used to study molecular assemblies. These findings, which are supported by a computational molecular dynamic study, demonstrate the uniqueness and added value of this NMR method. 相似文献
4.
In this paper, we consider a viscoelastic wave equation of variable coefficients in the presence of past history with nonlinear damping and delay in the internal feedback and dynamic boundary conditions. Under suitable assumptions, we establish an explicit and general decay rate result without imposing restrictive assumption on the behavior of the relaxation function at infinity by Riemannian geometry method and Lyapunov functional method. 相似文献
5.
电路过渡过程所列方程是微分方程,本文中采用的是方框图模型分析法,即将微分方程的复杂示解分解成最基本的加(减)、乘(除)、积分(微分)、增益等运算,采用VB设计用户界面产进行计算,并给出了一算例。 相似文献
6.
We consider a resource management problem in which the management objective is to minimize fluctuations in resource stocks. Stabilizing management policies constitute the designing of memoryless state feedback control strategies for a discrete time resource model which contains unknown but bounded fluctuations. We also show that the problem of maximizing sustainable yield in an uncertain fishery can be considered as the problem of stabilizing of the stock level.The paper corresponds to an invited talk at the 14th Symposium on Operations Research, Ulm, September 6–8, 1989.The support by Yrjö Jahnsson Foundation is gratefully acknowledged.This work was supported by NSF and AFOSR under grant ECS 8602524. 相似文献
7.
T. Temesvári C. De Dominicis I.R. Pimentel 《The European Physical Journal B - Condensed Matter and Complex Systems》2002,25(3):361-372
Symmetry considerations and a direct, Hubbard-Stratonovich type, derivation are used to construct a replica field-theory relevant
to the study of the spin glass transition of short range models in a magnetic field. A mean-field treatment reveals that two
different types of transitions exist, whenever the replica number n is kept larger than zero. The Sherrington-Kirkpatrick critical point in zero magnetic field between the paramagnet and replica
magnet (a replica symmetric phase with a nonzero spin glass order parameter) separates from the de Almeida-Thouless line,
along which replica symmetry breaking occurs. We argue that for studying the de Almeida-Thouless transition around the upper
critical dimension d = 6, it is necessary to use the generic cubic model with all the three bare masses and eight cubic couplings. The critical
role n may play is also emphasized. To make perturbative calculations feasible, a new representation of the cubic interaction is
introduced. To illustrate the method, we compute the masses in one-loop order. Some technical details and a list of vertex
rules are presented to help future renormalisation-group calculations.
Received 9 October 2001 相似文献
8.
Papert's (1978) appeal to reconsider the power and possibilities of the aesthetic in mathematics learning is often ignored in mathematics education research. This paper begins with the premise, put forth by Dewey (1934), that the aesthetic structures many dimensions of inquiry and experience. In the same way that using particular paintings, musical compositions, or even everyday experiences has been instrumental to attempts by philosophers to understand the aesthetic dimensions of meaning and experience in artistic domains, I propose that analysing a particular encounter with mathematics may help reveal the nature and role of the often nebulous responses of elegance, beauty, and `fit' to which mathematicians lay claim in their mathematical activity. To achieve this, I draw on and adapt the defining features of the aesthetic character of experience set forth by the aesthetician Beardsley (1982). This, in turn, sheds light on the role thataesthetics can play in mathematical inquiry and experience, and provides initial categories and conjectures that can be used to investigate the potential roles of aesthetics in mathematics learning contexts.This revised version was published online in September 2005 with corrections to the Cover Date. 相似文献
9.
10.
P. E. Cladis 《Journal of statistical physics》1991,62(5-6):899-925
We first discuss nonlinear aspects of phase transition theory applied to a particular liquid crystal phase transition. A simple derivation is given to show how two coupled Goldstone modes (one appearing as gauge fluctuations of the ordered phase) can force a phase transition, against all expectations, to take place discontinuously (theory of Halperin, Lubensky, and Ma)-but the discontinuity may be immeasurably small. Then, we describe a new dynamical test of phase transition order, developed by Cladiset al., that turns out to be more sensitive than x-ray diffraction and adiabatic calorimetry. Quantitative data found by this new method are in excellent agreement with the measurements of adiabatic calorimetry and x-ray diffraction as well as expectations implicit in the predictions of HLM.This is the text of an after-banquet talk given at the CNLS Workshop on the Dynamics of Concentrated Systems. 相似文献