Implementation of Dynamical Nucleation Theory Effective Fragment Potentials Method for Modeling Aerosol Chemistry

TitleImplementation of Dynamical Nucleation Theory Effective Fragment Potentials Method for Modeling Aerosol Chemistry
Publication TypeJournal Article
Year of Publication2011
AuthorsDevarajan A, Windus TL, Gordon MS
Journal TitleJournal of Physical Chemistry A
Date Published12
Type of ArticleArticle
ISBN Number1089-5639
Accession NumberWOS:000297445800001
Keywords2nd, BENZENE DIMER, clusters, distributed data interface, fluorination, molecules, photodissociation, sensitivity, transition-state theory, virial-coefficient, water

In this work, the dynamical nucleation theory (DNT) model using the ab initio based effective fragment potential (EFP) is implemented for evaluating the evaporation rate constant and molecular properties of molecular dusters. Predicting the nucleation rates of aerosol particles in different chemical environments is a key step toward understanding the dynamics of complex aerosol chemistry. Therefore, molecular scale models of nanoclusters are required to understand the macroscopic nucleation process. On the basis of variational transition state theory, DNT provides an efficient approach to predict nucleation kinetics. While most DNT Monte Carlo simulations use analytic potentials to model critical sized clusters, or use ab initio potentials to model very small clusters, the DNTEFP Monte Carlo method presented here can treat up to critical sized clusters using the effective fragment potential (EFP), a rigorous nonempirical intermolecular model potential based on ab initio electronic structure theory calculations, improvable in a systematic manner. The DNTEFP method is applied to study the evaporation rates, energetics, and structure factors of multicomponent clusters containing water and isoprene. The most probable topology of the transition state characterizing the evaporation of one water molecule from a water hexamer at 243 K is predicted to be a conformer that contains six hydrogen bonds, with a topology that corresponds to two water molecules stacked on top of a quadrangular (H(2)O)(4) cluster. For the water hexamer in the presence of isoprene, an increase in the cluster size and a 3-fold increase in the evaporation rate are predicted relative to the reaction in which one water molecule evaporates from a water hemmer cluster.

Alternate JournalJ. Phys. Chem. A