Vibrations and thermodynamics of clusters of polycyclic aromatic hydrocarbon molecules: the role of internal modes

The vibrational spectra of clusters of coronene molecules are theoretically calculated using a mixed quantum/classical scheme, each molecule being described by a tight-binding Hamiltonian, the intermolecular forces being provided by explicit Lennard-Jones and point charge sites. The normal modes of vibrations are shown to exhibit significant variations upon clustering. In particular, for large clusters intra- and intermolecular modes tend to mix and fill the mid-infrared range. We also calculate the heat capacity of the (C24H12)8 cluster as a function of temperature, emphasizing the isomerizations that take place during melting. Quantum delocalization effects, as obtained from the Pitzer-Gwinn semiclassical approximation, are important enough to wash out all signatures of the structural transitions on the caloric curve. On the basis of a simple two-state model we estimate that clusters containing about 300 molecules are required for melting to be detected on the caloric curve.     

A theoretical study of the H-abstraction reactions from HOI by moist air radiolytic products (H, OH, and O (3P)) and iodine atoms (2P(3/2))

The rate constants of the reactions of HOI molecules with H, OH, O ((3)P), and I ((2)P(3/2)) atoms have been estimated over the temperature range 300-2500 K using four different levels of theory. Geometry optimizations and vibrational frequency calculations are performed using MP2 methods combined with two basis sets (cc-pVTZ and 6-311G(d,p)). Single-point energy calculations are performed with the highly correlated ab initio coupled cluster method in the space of single, double, and triple (pertubatively) electron excitations CCSD(T) using the cc-pVTZ, cc-pVQZ, 6-311+G(3df,2p), and 6-311++G(3df,3pd) basis sets. Reaction enthalpies at 0 K were calculated at the CCSD(T)/cc-pVnZ//MP2/cc-pVTZ (n = T and Q), CCSD(T)/6-311+G(3df,2p)//MP2/6-311G(d,p), and CCSD(T)/6-311++G(3df,3pd)//MP2/6-311G(d,p) levels of theory and compared to the experimental values taken from the literature. Canonical transition-state theory with an Eckart tunneling correction is used to predict the rate constants as a function of temperature. The computational procedure has been used to predict rate constants for H-abstraction elementary reactions because there are actually no literature data to which the calculated rate constants can be directly compared. The final objective is to implement kinetics of gaseous reactions in the ASTEC (accident source term evaluation code) program to improve speciation of fission products, which can be transported along the reactor coolant system (RCS) of a pressurized water reactor (PWR) in the case of a severe accident.     

Thermodynamics of the formaldehyde-water and formaldehyde-ice systems for atmospheric applications

Formaldehyde (HCHO) is a species involved in numerous key atmospheric chemistry processes that can significantly impact the oxidative capacity of the atmosphere. Since gaseous HCHO is soluble in water, the water droplets of clouds and the ice crystals of snow exchange HCHO with the gas phase and the partitioning of HCHO between the air, water, and ice phases must be known to understand its chemistry. This study proposes thermodynamic formulations for the partitioning of HCHO between the gas phase and the ice and liquid water phases. A reanalysis of existing data on the vapor-liquid equilibrium has shown the inadequacy of the Henry's law formulation, and we instead propose the following equation to predict the mole fraction of HCHO in liquid water at equilibrium, X(HCHO,liq), as a function of the partial pressure P(HCHO) (Pa) and temperature T (K): X(HCHO,liq) = 1.700 × 10(-15)?e((8014/T))(P(HCHO))(1.105). Given the paucity of data on the gas-ice equilibrium, the solubility of HCHO and the diffusion coefficient (D(HCHO)) in ice were measured by exposing large single ice crystals to low P(HCHO). Our recommended value for D(HCHO) over the temperature range 243-266 K is D(HCHO) = 6 × 10(-12) cm(2) s(-1). The solubility of HCHO in ice follows the relationship X(HCHO,ice) = 9.898 × 10(-13)?e((4072/T))(P(HCHO))(0.803). Extrapolation of these data yields the P(HCHO) versus 1/T phase diagram for the H(2)O-HCHO system. The comparison of our results to existing data on the partitioning of HCHO between the snow and the atmosphere in the high arctic highlights the interplay between thermodynamic equilibrium and kinetics processes in natural systems.     

ChemInform Abstract: An ab initio Theoretical Study of the Electronic Structure of UO2+ and [UO2(CO3)3]5‐.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Monte Carlo versus molecular dynamics simulations in heterogeneous systems: an application to the n-pentane liquid-vapor interface

The Monte Carlo (MC) and molecular dynamics (MD) methodologies are now well established for computing equilibrium properties in homogeneous fluids. This is not yet the case for the direct simulation of two-phase systems, which exhibit nonuniformity of the density distribution across the interface. We have performed direct MC and MD simulations of the liquid-gas interface of n-pentane using a standard force-field model. We obtained density and pressure components profiles along the direction normal to the interface that can be very different, depending on the truncation and long range correction strategies. We discuss the influence on predicted properties of different potential truncation schemes implemented in both MC and MD simulations. We show that the MD and MC profiles can be made in agreement by using a Lennard-Jones potential truncated via a polynomial function that makes the first and second derivatives of the potential continuous at the cutoff distance. In this case however, the predicted thermodynamic properties (phase envelope, surface tension) deviate from experiments, because of the changes made in the potential. A further readjustment of the potential parameters is needed if one wants to use this method. We conclude that a straightforward use of bulk phase force fields in MD simulations may lead to some physical inconsistencies when computing interfacial properties.     

Photo‐Cross‐Linking Probes for Trapping G‐Quadruplex DNA

We have developed a straightforward synthetic pathway to a set of six photoactivatable G‐quadruplex ligands with a validated G4‐binding motif (the bisquinolinium pyridodicarboxamide PDC‐360A) tethered through various spacers to two different photo‐cross‐linking groups: benzophenone and an aryl azide. The high quadruplex‐versus‐duplex selectivity of the PDC core was retained in the new derivatives and resulted in selective alkylation of two well‐known G‐quadruplexes (human telomeric G4 and oncogene promoter c‐myc G4) under conditions of harsh competition. The presence of two structurally different photoactivatable functions allowed the selective alkylation of G‐quadruplex structures at specific nucleobases and irreversible G4 binding. The topology and sequence of the quadruplex matrix appear to influence strongly the alkylation profile, which differs for the telomeric and c‐myc quadruplexes. The new compounds are photoactive in cells and thus provide new tools for studying G4 biology.     

Stripping the latex: the challenge of miniemulsion polymerization without initiator,costabilizer and surfactant

When finally processed to provide the function for which the latex was selected―binding, protecting, finishing―components such as surfactant, costabilizer or initiator become generally useless, not to say detrimental. In this study, we show that miniemulsion photopolymerization provides a suitable method to create latex without the apparent addition of these three compounds. Indeed, UV-driven monomer self-initiation can create initiating radicals without the aid of initiator, the fast in situ photogenerated polymer can hinder Ostwald ripening with the assistance of external costabilizer, and finally, UV-transparent clay can replace conventional surfactant to ensure colloidal stabilization. Each strategy has been developed individually before being combined together to end up with a unique miniemulsion procedure free of initiator, costabilizer and surfactant. Such approach paves the way to a simplified and environmentally improved pathway towards aqueous polymer dispersions.     

Acrylate nanolatex via self‐initiated photopolymerization

The use of UV light to initiate emulsion polymerization processes is generally overlooked, whilst extensive literature exists on photocuring of monomer films. In this study, the unique potential of UV light to produce at ambient temperature polyacrylate latexes without initiator was exploited. Although radical initiators are utilized at low concentration, their cost, toxicity, and odor provide incentives for finding alternatives. Starting with concentrated (30 wt %) and low scattering acrylate miniemulsions (droplet diameter <100 nm), it was demonstrated that acrylate self‐initiation can promote an efficient and fast photopolymerization in micrometer‐scale reactor (spectrophotometric cell) and lab‐scale photoreactor. Herein, all kinetic, colloidal, and mechanistic aspects involved in the self‐initiation of acrylate miniemulsion were extensively examined to provide a complete picture. In particular, the effects of droplet size, initiating wavelength, optical path, and irradiance on the course of the polymerization were thoroughly discussed. A diradical self‐initiation pathway is the most likely mechanism. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1843–1853