Simulation calculation of dielectric constants: Comparison of methods on an exactly solvable model

A mean spherical model of classical dipoles on a simple cubic lattice of sideM=2N+1 sites is considered. Exact results are obtained for finite systems using periodic boundary conditions with an external dielectric constant and using reaction field boundary conditions with a cutoff radiusR _c N and an external dielectric constant. The dielectric constant in the disordered phase is calculated using a variety of fluctuation formulas commonly implemented in Monte Carlo and molecular dynamics simulations of dipolar systems. The coupling in the system is measured by the parametery=4 ²/9kT, where ² is the fixed mean square value of the dipole moments on the lattice. The system undergoes a phase transition aty2.8, so that very high dielectric constants cannot be obtained in the disordered phase. The results show clearly the effects of system size, cutoff radius, external dielectric constant, and different measuring techniques on a dielectric constant estimate. It is concluded that with periodic boundary conditions, the rate of approach of the dielectric constant estimate to its thermodynamic limit is asN ^–2/3 and depends only weakly on. Methods of implementing reaction field boundary conditions to give rapid convergence to the thermodynamic limit are discussed.     

Formation of isoprostane bicyclic endoperoxides from the autoxidation of cholesteryl arachidonate

Autoxidation of polyunsaturated fatty acids and esters leads to a complex mixture containing hydroperoxides and cyclic peroxides. Prostaglandin bicyclic endoperoxides have been detected from the autoxidation of cholesteryl arachidonate by LC-MS and GC-MS techniques. All four possible types (I-IV) of bicyclic endoperoxides have been found starting from different regioisomeric hydroperoxides of cholesteryl arachidonate. Furthermore, the stereochemistry of Type IV bicyclic endoperoxides has been determined by conversion to pentafluorobenzyl (PFB) ester, trimethylsilyl (TMS) derivatives, and comparison with synthetic standards by the use of GC-MS. All eight possible diastereomers of the derivatized isoprostanes were observed and were separated by gas chromatography. The bicyclic endoperoxides with the two alkyl chains syn on the cyclopentane ring were formed preferentially to those with anti configuration, a result anticipated from earlier work. Substantial amounts of the anti-substituted isoprostanes, including PGF(2)(alpha), were, however, observed in the product mixture.     

Photochemical Characteristics of the mode-locking dyes 1,1′-diethyl-4,4′ carbocyanine iodide (cryptocayanine,DCI) and 1,1′-diethyl-2,2′ dicarb

The fluorescence quantum efficiencies, lifetimes and triplet—triplet absorption spectra of the cyanine dyes DCI     

Invariance principles for Gaussian sequences

An almost sure invariance principle is proved for stationary Gaussian sequences whose covariances r(n) satisfy r(n) = O (n ^–1–)for some >0.