title: Properties and structure of aromatic ester solvents.
abstract: This paper reports on an experimental and theoretical study of the aromatic ester solvents family. Several compounds were selected to analyze the different factors that influence their liquid-state properties and structures. The pressure-volume-temperature behavior of these fluids was measured accurately over wide temperature and pressure ranges and correlated successfully with the empirical TRIDEN equation. From the measured data the relevant derived coefficients of isothermal compressibility, isobaric expansibility, and internal pressure were calculated. The statistical associating fluid theory (SAFT) and perturbed chain statistical associating fluid theory (PC-SAFT) molecularly based equations of state were used to predict the PVT behavior with model parameters obtained from the correlation of available saturation literature data; the results provided by PC-SAFT equations of state were clearly superior for all of the studied solvents. The fluid's molecular level structure was studied by quantum computations at the B3LYP/6-311++g** level and classical molecular dynamics simulations in the NPT ensemble with the OPLS-AA forcefield. Molecular parameters, such as torsional barriers or cluster energetics, were analyzed as a function of ester structures. The molecular dynamics study provides, on one hand, theoretical values of thermophysical properties, which are compared with the experimental ones, and, on the other hand, valuable molecular level structural information. On the basis of both macroscopic and microscopic studies complex fluid structures were inferred with important effects arising from the geometries of the studied molecules and from the existence of remarkable intermolecular forces of dominating dipolar nature.
authors.affiliation: Departamento de Química, Universidad de Burgos, 09001 Burgos, Spain. sapar@ubu.es
authors.forename: Santiago
authors.initials: S
authors.lastname: Aparicio
authors.forename: Rafael
authors.initials: R
authors.lastname: Alcalde
authors.forename: María J
authors.initials: MJ
authors.lastname: Dávila
authors.forename: Begoña
authors.initials: B
authors.lastname: García
authors.forename: José M
authors.initials: JM
authors.lastname: Leal