Thermodynamic properties of a molecular dipolar liquid using the two-phase thermodynamic approach.

A modified version of the original two-phase thermodynamic approach has been extended to evaluate the thermodynamic properties of molecular systems. Its basic assumption states that the density of states can be decomposed into solid-like and gas-like components. The solid part has been approximated by that of a set of harmonic oscillators, whereas a subset composed of rough hard spheres has been considered for the gas part.

Free energy and entropy of a dipolar liquid by computer simulations.

Thermodynamic properties for a system composed of dipolar molecules are computed. Free energy is evaluated by means of the thermodynamic integration technique, and it is also estimated by using a perturbation theory approach, in which every molecule is modeled as a hard sphere within a square well, with an electric dipole at its center. The hard sphere diameter, the range and depth of the well, and the dipole moment have been calculated from properties easily obtained in molecular dynamics simulations.

Influence of hydrogen bonds and temperature on dielectric properties.

Dielectric properties are evaluated by means of molecular dynamics simulations on two model systems made up of dipolar molecules. One of them mimics methanol, whereas the other differs from the former only in the ability to form hydrogen bonds. Static dielectric properties such as the permittivity and the Kirkwood factor are evaluated, and results are analyzed by considering the distribution of relative orientations between molecular dipoles.

Rotational dynamics of a dipolar supercooled liquid.

We study the rotational dynamics of a supercooled molecular liquid by means of molecular dynamics simulations. The system under investigation is composed of rigid diatomic molecules with an associate dipole moment. At room temperature, orientational correlations decrease rapidly with increasing distances.

Microscopic dynamics of supercooled low weight alcohols.

Dynamical properties of low weight alcohols have been analyzed both in the liquid and the supercooled states. Realistic interatomic potential models for methanol and ethanol have been used. The influence of temperature on the hydrogen-bonded structure has been undertaken.

Study of spatial correlations in a supercooled molecular system.

Spatial heterogeneities have been investigated in a supercooled system composed of diatomic molecules with an associated dipole moment by using the molecular dynamics simulation technique. Pair distribution functions of molecules with different mobilities have been evaluated, and it has been found that molecules belonging to the same dynamic domain are spatially correlated. Molecules with extremely large mobilities form larger clusters than those resulting from random statistics.

Dynamic heterogeneities in a supercooled diatomic molecular system.

Dynamic heterogeneities in a supercooled system of diatomic molecules with an associated dipole moment have been investigated. To this end, three-time correlation functions have been evaluated. Correlations between molecular displacements performed during consecutive time intervals are apparent at low temperatures in the beta -relaxation regime, whereas they tend to disappear during the alpha -relaxation regime.

On the analysis of conformational dynamics in polymers with several rotational isomers.

The ability of different correlation functions to shed some light onto the conformational dynamics of an amorphous polymer has been analyzed. The study has been performed on a polyethylene model polymer, which has been simulated at decreasing temperatures towards its glass transition, via the molecular dynamics technique. Three rotational isomers are allowed by the considered torsional potential.

The role of hydrogen bonding in supercooled methanol.

The role of hydrogen bonding on the microscopic properties of supercooled methanol has been analyzed by means of molecular dynamics simulations. Thermodynamic, structural, and dynamical properties have been investigated in supercooled methanol. The results have been compared with those of an ideal methanol-like system whose molecules have the same dipole moment as the methanol but lack sites for hydrogen bonding.