Monte Carlo Simulations of Small Sulfuric Acid-water Clusters
Effective atom-atom potentials are developed for binary sulfuric acid-water clusters and applied in a Bennett Metropolis Monte Carlo calculation to determine free energy differences for small neighboring sized clusters of fixed composition at 298 K. The atom-atom pair potentials consist of Lennard-Jones short-range and Coulombic long-range terms and assume rigid SO42δ- with two unconstrained Hδ+ and rigid H2O molecules interacting via revised central force (RSL2) potentials. The potential parameters are determined from both ab initio studies and tests of the potential using the statistical mechanical formalism for binary cluster size distributions. In the potential tests, fixed composition free energy differences, δ fkm,m, for [H2O]km[H2SO4]m clusters are plotted versus (km + m)-1/3, and the resulting slope and intercept (in the large cluster regime) are used to extract model dependent binary liquid surface tension and partial vapor pressures at 298 K. The potential parameters are adjusted to obtain approximate agreement with experimental surface tension and partial vapor pressures for k = 1 and 4 (84% and 57% weight percent H2SO4, respectively). The free energy differences for m ≤ 15 are presented, together with internal cluster energy contributions, snapshots of cluster structure, and evidence for onset of the large cluster regime near m = 5. The long-range goals have been to test the free energy difference procedure for studying binary cluster properties and to develop model potentials appropriate for the simulation of small binary clusters at low temperatures characteristic of stratospheric sulfuric acid-water aerosols.
S. M. Kathmann and B. N. Hale, "Monte Carlo Simulations of Small Sulfuric Acid-water Clusters," Journal of Physical Chemistry B, vol. 105, no. 47, pp. 11719-11728, American Chemical Society (ACS), Oct 2001.
The definitive version is available at https://doi.org/10.1021/jp0116499
Keywords and Phrases
Binary Clusters; Aerosols; Computer Simulation; Free Energy; Monte Carlo Methods; Sulfuric Acid; Surface Tension; Thermal Effects; Water; Molecular Dynamics
International Standard Serial Number (ISSN)
Article - Journal
© 2001 American Chemical Society (ACS), All rights reserved.
01 Oct 2001