The effect of functional groups on the glass transition temperature of atmospheric organic compounds: a molecular dynamics study.

Organic compounds constitute a substantial part of atmospheric particulate matter not only in terms of mass concentration but also in terms of distinct functional groups. The glass transition temperature provides an indirect way to investigate the phase state of the organic compounds, playing a crucial role in understanding their behavior and influence on aerosol processes. Molecular dynamics (MD) simulations were implemented here to predict the glass transition temperature () of atmospherically relevant organic compounds as well as the influence of their functional groups and length of their carbon chain.

Geometric Analysis of Free and Accessible Volume in Atmospheric Nanoparticles.

Computer-generated atomistic microstructures of atmospheric nanoparticles are geometrically analyzed using Delaunay tessellation followed by Monte Carlo integration to compute their free and accessible volume. The nanoparticles studied consist of -pinonic acid (a biogenic organic aerosol component), inorganic ions (sulfate and ammonium), and water. Results are presented for the free or unoccupied volume in different domains of the nanoparticles and its dependence on relative humidity and organic content.

Excluded-Volume Interactions in Field-Theoretic Simulations: Multiconvolutions and Model Equivalence.

To deal with divergences of functional integrals in field-theoretic simulations (FTS) of complex fluids, the microscopic density is often smeared by being replaced by a convoluted one, typically using a Gaussian masking function. The smearing changes radically the nature of nonbonded interactions of the original microscopic density and results in a regularized model that is free of ultraviolet (UV) divergences. In this work, we first resolve a few fundamental issues related with the use of masking functions for δ-interactions in FTS and then we detail a new methodology that builds on the concept of multiconvoluted inverse potentials and a principle of model equivalence for statistical weights to accommodate more physically relevant interactions in FTS.

Coarse-Grained Model Incorporating Short- and Long-Range Effective Potentials for the Fast Simulation of Micelle Formation in Solutions of Ionic Surfactants.

A coarse-grained model comprising short- and long-range effective potentials, parametrized with the iterative Boltzmann inversion (IBI) method, is presented for capturing micelle formation in aqueous solutions of ionic surfactants using as a model system sodium dodecyl sulfate (SDS). In the coarse-grained (CG) model, each SDS molecule is represented as a sequence of four beads while each water molecule is modeled as a single bead. The proposed CG scheme involves ten potential energy functions: four of them describe bonded interactions and control the distribution functions of intramolecular degrees of freedom (bond lengths, valence angles, and dihedrals) along an SDS molecule while the other six account for intermolecular interactions between pairs of SDS and water beads and control the radial distribution functions.

Direct calculation of the functional inverse of realistic interatomic potentials in field-theoretic simulations.

We discuss the functional inverse problem in field-theoretic simulations for realistic pairwise potentials such as the Morse potential (widely used in particle simulations as an alternative to the 12-6 Lennard-Jones one), and we propose the following two solutions: (a) a numerical one based on direct inversion on a regular grid or deconvolution and (b) an analytical one by expressing attractive and repulsive contributions to the Morse potential as higher-order derivatives of the Dirac delta function; the resulting system of ordinary differential equations in the saddle-point approximation is solved numerically with appropriate model-consistent boundary conditions using a Newton-Raphson method. For the first time, exponential-like, physically realistic pair interactions are analytically treated and incorporated into a field-theoretic framework. The advantages and disadvantages of the two approaches are discussed in detail in connection with numerical findings from test simulations for the radial distribution function of a monatomic fluid at realistic densities providing direct evidence for the capability of the analytical method to resolve structural features down to the Angstrom scale.