scholarly journals The symmetry principle of antiaromaticity

2020 ◽  
Vol 75 (4) ◽  
pp. 327-339 ◽  
Author(s):  
Raphael J. F. Berger ◽  
Alexandre Viel

AbstractCurrent definitions of aromaticity are purely phenomenological and relate symmetry, reactive stability and the occurrence of molecular diamagnetic response currents. The antithetical concept of antiaromaticity provides a connection between the contrary properties: structural instability or distortion out of higher symmetry, a small HOMO-LUMO gap, and paramagnetic response currents. We reveal the symmetry principle that is underlying antiaromaticity by showing an intimate and strict symmetry induced relation between these properties. The principle is mathematically rigorous and can be formulated like: First order (and related) Jahn-Teller distorted molecules out of non-cubic and non-icosahedral point groups are prone to induced paramagnetism in magnetic fields parallel to the main axis of symmetry. We show by the exemplary cases of cyclobutadiene, cyclcooctatetraene, pentalene and manganese trifluoride how this principle works and discuss this new perspective on antiaromaticity.

1992 ◽  
Vol 57 (9) ◽  
pp. 1951-1959 ◽  
Author(s):  
Madlene L. Iskander ◽  
Samia A. El-Abbady ◽  
Alyaa A. Shalaby ◽  
Ahmed H. Moustafa

The reactivity of the base induced cyclodimerization of 1-(6-arylpyridazin-3-yl)-3-oxidopyridinium chlorides in a pericyclic process have been investigated kinetically at λ 380 nm. The reaction was found to be second order with respect to the liberated betaine and zero order with respect to the base. On the other hand dedimerization (monomer formation) was found to be first order. It was shown that dimerization is favoured at low temperature, whereas dedimerization process is favoured at relatively high temperature (ca 70 °C). Solvent effects on the reaction rate have been found to follow the order ethanol > chloroform ≈ 1,2-dichloroethane. Complete dissociation was accomplished only in 1,2-dichloroethane at ca 70 °C. The thermodynamic activation parameters have been calculated by a standard method. Thus, ∆G# has been found to be independent on substituents and solvents. The high negative values of ∆S# supports the cyclic transition state which is in favour with the concerted mechanism. MO calculations using SCF-PPP approximation method indicated low HOMO-LUMO energy gap of the investigated betaines.


2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Wesley Fussner ◽  
Mai Gehrke ◽  
Samuel J. van Gool ◽  
Vincenzo Marra

Abstract We provide a new perspective on extended Priestley duality for a large class of distributive lattices equipped with binary double quasioperators. Under this approach, non-lattice binary operations are each presented as a pair of partial binary operations on dual spaces. In this enriched environment, equational conditions on the algebraic side of the duality may more often be rendered as first-order conditions on dual spaces. In particular, we specialize our general results to the variety of MV-algebras, obtaining a duality for these in which the equations axiomatizing MV-algebras are dualized as first-order conditions.


Mathematics ◽  
2021 ◽  
Vol 9 (13) ◽  
pp. 1519
Author(s):  
Mikulas Huba ◽  
Pavol Bistak ◽  
Damir Vrancic ◽  
Katarina Zakova

The article reviews the results of a number of recent papers dealing with the revision of the simplest approaches to the control of first-order time-delayed systems. The concise introductory review is extended by an analysis of two discrete-time approaches to dead-time compensation control of stable, integrating, and unstable first-order dead-time processes including simple diagnostics of the model used and focusing on the possibility of simplified but reliable plant modelling. The first approach, based on the first historically known dead-time compensator (DTC) with possible dead-beat performance, is based on the reconstruction of the actual process variables and the compensation of input disturbances by an extended state observer (ESO). Such solutions play an important role both in a disturbance observer (DOB) based control and in an active disturbance rejection control (ADRC). The second approach considered comes from the Smith predictor with two degrees of freedom, which combines feedforward control with output disturbance reconstruction and compensation by the parallel plant model. It is shown that these two approaches offer advantageous properties in the case of actuator limitations, in contrast to the commonly used PID controllers. However, when applied to integrating and unstable first-order systems, the unconstrained and possibly unobservable output disturbance signal of the second solution must be eliminated from the control loop, due to the hidden structural instability of the Smith predictor-like solutions. The modified solutions, usually referred to as filtered Smith predictor (FSP), then no longer provide a disturbance signal and thus no longer fully fit into the concept of Industry 4.0, which is focused on further optimization, predictive maintenance in dynamic systems, diagnosis, fault detection and fault identification of dynamic processes and forms the basis for the digitalization of smart production. Nevertheless, the detailed analysis of the elimination of the unstable disturbance response mode is also worth mentioning in terms of other possible solutions. The application of both approaches to the control of a thermal process shows almost equivalent quality, but with different dependencies on the tuning parameters used. It is confirmed that a more detailed identification of the controlled process and the resulting higher complexity of the control algorithms does not necessarily lead to an increase in the resulting quality of the transients, which underlines the importance of the simplified plant modelling for practice.


2005 ◽  
Vol 60 (6) ◽  
pp. 593-596 ◽  
Author(s):  
Xiaohui Liu ◽  
Martial Aime Wankeu ◽  
Heiko Lueken ◽  
Richard Dronskowski

Well-crystallized copper carbodiimide, CuNCN, was synthesized by the slow oxidation of a copper(I) cyanamide precursor under aqueous conditions. The X-ray powder data evidence the orthorhombic system and space group Cmcm with a = 2.9921(1), b = 6.1782(1), c = 9.4003(2) Å , V = 173.769(5) Å3 and Z = 4. There is a strongly distorted octahedral Cu2+ coordination reflecting a typical first-order Jahn-Teller effect, with interatomic distances of 4×Cu-N = 2.001(2) Å and 2×Cu-N = 2.613(3) Å ; the NCN2− unit adopts the carbodiimide shape with C-N = 1.227(4) Å . Despite the formal d9 electron count of Cu2+, CuNCN exhibits a small temperature-independent paramagnetism and is likely to be a metallic conductor.


2014 ◽  
Vol 90 (10) ◽  
Author(s):  
Patrick G. Reuvekamp ◽  
Reinhard K. Kremer ◽  
Jürgen Köhler ◽  
Annette Bussmann-Holder

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