Transferable potentials for phase equilibria. 8. United-atom description for thiols, sulfides, disulfides, and thiophene

An extension of the transferable potentials for phase equilibria united-atom (TraPPE-UA) force field to thiol, sulfide, and disulfide functionalities and thiophene is presented. In the TraPPE-UA force field, nonbonded interactions are governed by a Lennard-Jones plus fixed point charge functional form. Partial charges are determined through a CHELPG analysis of electrostatic potential energy surfaces derived from ab initio calculations at the HF/6-31g+(d,p) level. The Lennard-Jones well depth and size parameters for four new interaction sites, S (thiols), S(sulfides), S(disulfides), and S(thiophene), were determined by fitting simulation data to pure-component vapor-equilibrium data for methanethiol, dimethyl sulfide, dimethyl disulfide, and thiophene, respectively. Configurational-bias Monte Carlo simulations in the grand canonical ensemble combined with histogram-reweighting methods were used to calculate the vapor-liquid coexistence curves for methanethiol, ethanethiol, 2-methyl-1-propanethiol, 2-methyl-2-propanethiol, 2-butanethiol, pentanethiol, octanethiol, dimethyl sulfide, diethyl sulfide, ethylmethyl sulfide, dimethyl disulfide, diethyl disulfide, and thiophene. Excellent agreement with experiment is achieved, with unsigned errors of less than 1% for saturated liquid densities and less than 3% for critical temperatures. The normal boiling points were predicted to within 1% of experiment in most cases, although for certain molecules (pentanethiol) deviations as large as 5% were found. Additional calculations were performed to determine the pressure-composition behavior of ethanethiol+n-butane at 373.15 K and the temperature-composition behavior of 1-propanethiol+n-hexane at 1.01 bar. In each case, a good reproduction of experimental vapor-liquid equilibrium separation factors is achieved; both of the coexistence curves are somewhat shifted because of overprediction of the pure-component vapor pressures.     

Simulation on the response of new phosphate glass RPC for <Emphasis Type="Italic">γ</Emphasis>-rays and e<Superscript>+</Superscript>/e<Superscript>−</Superscript> particles using GEANT3

The influence of phosphate glass electrode in the configuration of resistive plate chamber has been studied using GEANT3.21 Monte Carlo code. Bakelite electrodes were replaced by phosphate glass electrodes, as these glass materials have low bulk resistivity, are portable and easy to handle. These types of RPCs in their compact form of all materials are suitable for high rate background environment. We find that these new types of RPCs give little higher response to γ-rays and e⁺/e⁻ particles, both for single-and double gap RPCs. The results of simulation are discussed.      

On generalising Abraham-Lorentz equation

It is proved that runaway solutions persist if Abraham's force –m is generalised by adding to it afinite number of terms which are linear in higher derivatives of . The implication of this result to Eliezer's relativistic generalisation of the Lorentz-Dirac equation is discussed.Worked supported by the Minerva Foundation.     

Recognition of critical pairs of polycyclic aromatics on crystalline, liquid-crystalline and isotropic regions of silica-supported polymer in HPLC

Summary The silica-supported comb-shaped polymer (Sil-ODA₁₈) with a “crystalline-to-isotropic” phase transition showed the characteristic behaviors of both polymeric and monomeric ODS phases. This was examined using a SRM 869 test mixture. Furthermore, Sil-ODA₁₈ exhibited a specific selectivity towards the critical pairs of polycyclic aromatic hydrocarbons (PAHs), such as acenaphthene and fluorene, or benz(a)anthracene and chrysene, or benzo(ghi)perylene, indeno(1,2,3-cd)pyrene and dibenz(a,h)anthracene. The separation of these solutes was controlled by selecting temperature and solvent systems. The selectivity on Sil-ODA₁₈ was also compared with a conventional ODS (octadecylsilyl silica gel) column. The selectivity on a Sil-ODA₁₈ matrix is attributable to an orientation change of the long-chain alkyl substituents on the surface of the silica base material on transition from crystalline to isotropic state.     

FRW Cosmology with Variable G and Λ

We have considered a cosmological model of the FRW universe with variable G and Λ. The solutions have been obtained for flat model with particular form of cosmological constant. The cosmological parameters have also been obtained for dust, radiation and stiff matter. The statefinder parameters are analyzed and have shown that these depends only on w and ε. Further the lookback time, proper distance, luminosity distance and angular diameter distance have also been calculated for our model.