The cyclodimerisation of 3-methyl-2-butenenitrile

3-Methyl-2-butenenitrile (1) cyclodimerised on treatment with lithium diisopropylamide in dimethoxyethane at temperatures between ?78°C and 0°C to 3-amino-4-cyano-1,5,5-trimethyl-1,3-cyclohexadiene (2) the structure of which was established by acid hydrolysis to the known 4-cyano-1,5,5-trimethyl-1-cyclohexene-3-one (3).     

Parametrically driven dark solitons

We show that unlike the bright solitons, the parametrically driven kinks are immune from instabilities for all dampings and forcing amplitudes; they can also form stable bound states. In the undamped case, the two types of stable kinks and their complexes can travel with nonzero velocities.     

Conical parametric scattering of a single extraordinary beam in BaTiO3 crystal

In this paper, the parametric scattering of a single extraordinary polarized beam of laser in BaTiO₃ photorefractive crystal has been investigated experimentally and theoretically. The resulting pattern consists of beam fanning, isotropic ring, and anisotropic one. Among all parts of scattering pattern, isotropic ring has not been studied as much as beam fanning and anisotropic ring, and there still are some differences in reports about it. Therefore, the study has mainly focused on this part. In this experimental configuration, isotropic ring is just visible in positive angles although the other parts of parametric scattering pattern can be visible from behind and in front of the crystal. In addition to steady state pattern in forward and backward directions, its transient behavior with the rotation of crystal has been studied. The results of experiments have been analyzed carefully, and their theoretical explanations have been presented based on the standard theory of parametric scattering in photorefractive crystals. It has been shown that this configuration corresponds to the so called parametric B-process scattering.     

A DFT investigation of anthocyanidins

A theoretical analysis of anthocyanidins, a class of natural plant pigments, has been conducted using density functional theory at the B3LYP/6-31G(d) level. It is found that these compounds are non-planar, with the 2-phenyl ring twisted relative to the benzopyrylium rings. TD-DFT calculations reveal a first excited state dominated by two orbital transitions, including the HOMO–LUMO transition. From a comparison of these molecular orbitals with those of related compounds, and from the known chemistry of these compounds, it is suggested that anthocyanidins should be regarded as natural, stable carbocations.     

Canonical Proper-Time Formulation of Relativistic Particle Dynamics. II

Our purpose in this paper is to provide theframework for a generalization of classical mechanicsand electrodynamics, including Maxwell's theory, whichis simple, technically correct, and requires noadditional work for the quantum case. We first show thatthere are two other definitions of proper-time, eachhaving equal status with the Minkowski definition. Weuse the first definition, called the proper-velocity definition, to construct a transformationtheory which fixes the proper-time of a given physicalsystem for all observers. This leads to a new invariancegroup and a generalization of Maxwell's equations left covariant under the action of this group.The second definition, called the canonical variablesdefinition, has the unique property that it isindependent of the number of particles. This definition leads to a general theory of directlyinteracting relativistic particles. We obtain theLorentz force for one particle (using its proper-time),and the Lorentz force for the total system (using theglobal proper-time). Use of the global proper-time tocompute the force on one particle gives the Lorentzforce plus a dissipative term corresponding to thereaction of this particle back on the cause of itsacceleration (Newton's third law). The wave equation derivedfrom Maxwell's equations has an additional term, firstorder in the proper-time. This term arisesinstantaneously with acceleration. This shows explicitly that the longsought origin of radiationreaction is inertial resistance to changes in particlemotion. The field equations carry intrinsic informationabout the velocity and acceleration of the particles in the system. It follows that our theory isnot invariant under time reversal, so that the existenceof radiation introduces an arrow for the (proper-time ofthe) system.     

Temperature dependent deuterium quadrupole coupling constants of short hydrogen bonds

Very short hydrogen bonds universally show large positive dependences of the deuterium NMR quadrupolar coupling constant with temperature. We present temperature dependent NMR data for eight such systems, with OO distances of between 238 and 250 pm, and show we can model the temperature dependences by density functional methods, as long as proper attention is paid to intermolecular effects and intermode couplings.     

Self-chemical ionization of diethylzinc

The self-chemical ionization of diethylzinc is examined by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and semiempirical molecular orbital calculations. Electron impact of diethylzinc neutral produces the radical cation, C(4)H(15)Zn(+) (m/z x 122), which reacts further with the neutral (C(2)H(5))(2)Zn to give the following product ions: Zn(+) (m/z x 64), C(2)H(5)Zn(+) (m/z x 93), C(4)H(9)Zn(+) (m/z x 121), C(4)H(11)Zn(2)(+) (m/z x 187), and C(6)H(15)Zn(2)(+) (m/z x 215). To determine the structure and pathways for production of these ions, monoisotopic (12)C(4)H(15)(64)Zn(+), (64)Zn(+) and (12)C(2)H(5)(64)Zn(+) were individually isolated and reacted with the neutral background. We also performed semiempirical molecular orbital calculations (ZINDO/1). The molecular orbital calculations and experimental data are consistent in predicting that the ethyl group on the diethylzinc cation carries the positive charge. Copyright 1999 John Wiley & Sons, Ltd.     

Smooth curve interpolation

In a recent paper [1] a method was presented for smooth curve interpolation by means of minimising the energy of an idealised elastic beam constrained to pass through given data points. This method of obtaining the curve required an enormous amount of computation, since it involved the repeated solution of a fourth order differential equation and the minimisation of a function of many variables, the number of variables being equal to the number of data points. In this paper a much simpler method is presented for finding the minimum energy curve in which the minimisation procedure is eliminated. An ALGOL procedure to perform the curve fit is supplied.