Density functional and Monte Carlo studies of sulfur. II. Equilibrium polymerization of the liquid phase

The equilibrium polymerization of sulfur is investigated by Monte Carlo simulations. The potential energy model is based on density functional results for the cohesive energy, structural, and vibrational properties as well as reactivity of sulfur rings and chains [Part I, J. Chem. Phys. 118, 9257 (2003)]. Liquid samples of 2048 atoms are simulated at temperatures 450less than or equal toTless than or equal to850 K and P=0 starting from monodisperse S-8 molecular compositions. Thermally activated bond breaking processes lead to an equilibrium population of unsaturated atoms that can change the local pattern of covalent bonds and allow the system to approach equilibrium. The concentration of unsaturated atoms and the kinetics of bond interchanges is determined by the energy DeltaE(b) required to break a covalent bond. Equilibrium with respect to the bond distribution is achieved for 15less than or equal toDeltaE(b)less than or equal to21 kcal/mol over a wide temperature range (Tgreater than or equal to450 K), within which polymerization occurs readily, with entropy from the bond distribution overcompensating the increase in enthalpy. There is a maximum in the polymerized fraction at temperature T-max that depends on DeltaE(b). This fraction decreases at higher temperature because broken bonds and short chains proliferate and, for Tless than or equal toT(max), because entropy is less important than enthalpy. The molecular size distribution is described well by a Zimm-Schulz function, plus an isolated peak for S-8. Large molecules are almost exclusively open chains. Rings tend to have fewer than 24 atoms, and only S-8 is present in significant concentrations at all T. The T dependence of the density and the dependence of polymerization fraction and degree on DeltaE(b) give estimates of the polymerization temperature T-f=450+/-20 K. (C) 2003 American Institute of Physics.

Equilibrium polymerization of cyclic carbonate oligomers. II. Role of multiple active sites

Ring opening polymerization of bisphenol A polycarbonate is studied by Monte Carlo simulations of a model comprising a fixed number of Lennard-Jones particles and harmonic bonds [J. Chem. Phys. 115, 3895 (2001)]. Bond interchanges produced by a low concentration (0.10%less than or equal toc(a)less than or equal to0.36%) of chemically active particles lead to equilibrium polymerization. There is a continuous transition in both 2D and 3D from unpolymerized cyclic oligomers at low density to a system of linear chains at high density, and the polymeric phase is much more stable in three dimensions than in two. The steepness of the polymerization transition increases rapidly as c(a) decreases, suggesting that it is discontinuous in the limit c(a)-->0. The transition is entropy driven, since the average potential energy increases systematically upon polymerization, and there is a steady decline in the degree of polymerization as the temperature is lowered. The mass distribution functions for open chains and for rings are unimodal, with exponentially decaying tails that can be fitted by Zimm-Schulz functions and simpler exponential forms. (C) 2002 American Institute of Physics.

England, Neo-Latin, and the Continental Journey: Linguistic and Textual Itineraries

This chapter examines the ramifications of continental travel and associated epistolary communication for English poets of the period. It argues that recourse to neo-Latin, the universal language of diplomacy, served not only to establish a sense of shared space—linguistic, cultural, generic—between England and the continent, but also to signal self-conscious differences (climatic, geographical, historical, political) between England and her continental peers. Through an investigation of a range of ‘performances’ on stages that were ‘academic’, poetic, autobiographical, and epistolographic, it assesses the central role of neo-Latin as a language that underwent a series of textual itineraries. These ‘itineraries’ manifest themselves in a number of ways. Neo-Latin as a shared linguistic medium can facilitate, and quite uniquely so, intertextual engagement with the classics, but now ancient Rome, its language, its mythology, its hierarchy of genres, are viewed through a seventeenth-century lens and appropriated by poets in both England and Italy to describe contemporary events, whether personal, or political. Close examination of the neo-Latin poetry of Milton and Marvell reveals, it is argued, a self-fashioning coloured by such textual itineraries and interchanges. The absorption and replication of continental literary and linguistic methodologies (the academic debate; the etymological play of Marinism; the hybridity of neo-Latin and Italian voices) reveal in short a linguistic and textual reciprocity that gave birth to something very new.