Molecular modeling of Al 3+ and benzene interactions with Suwannee fulvic acid

Abstract

The effects that Al 3+ and benzene interactions exhibit on a model fulvic acid were investigated. Energy minimizations of the structures mimicking the interactions of Al 3+–Suwannee fulvic acid (SFA), benzene–SFA and Al 3+–benzene–SFA were run with a solvation sphere of 60 H 2O molecules with the semi-empirical methods PM3 and PM5. The semi-empirical method PM3 was run with Gaussian 98 and CAChe Workstation Pro 6.1.1 to compare the results of the energy minimization algorithms in the two programs. PM5 calculations were run with CAChe Workstation Pro 6.1.1. Molecular dynamics (MD) simulations were run in Cerius 2 (Accelrys Inc., San Diego, CA) using the Universal Force Field (UFF) 1.02 [Rappé A. K., Casewit C., Colwell K., Goddard W., and Skiff W. (1992) UFF, a full periodic-table force-field for molecular mechanics and molecular dynamics simulations. J. Am. Chem. Soc. 114(25), 10024–10035] and COMPASS force field [Sun H. (1998) COMPASS: an ab initio force-field optimized for condensed-phase applications—overview with details on alkane and benzene compounds. J. Phys. Chem. B 102, 7338–7364]. Single point calculations were run on the minimized structures at the B3LYP/6-31G(d) level to obtain more accurate estimates of the energy on the minimized structures derived from the PM3, PM5, and UFF methods and to normalize energies to the same reference state. This methodology was used as the standard of comparison for all the models to assess whether or not a given configuration was reasonably stable. The PM3/G03 energy minimizations predicted the lowest B3LYP/6-31G(d) potential energies of the methodologies examined in this study. Thus, this method is considered the most reliable of those tested. The PM3/G03 method predicted that there would be aromatic–aromatic interactions between benzene and SFA. The presence of Al 3+ was predicted not to interfere with aromatic–aromatic interactions between benzene and SFA, but benzene may influence the location of metal complexation to SFA.