Evaluation of density functional theory methods for studying chemisorption of arsenite on ferric hydroxides

Understanding adsorption of arsenic on ferric hydroxide surfaces is important for predicting the fate of arsenic in the environment and in designing treatment systems for removing arsenic from potable water. This research investigated the binding of arsenite to ferric hydroxide clusters using several density functional theory methods. Comparison of calculated and experimentally measured As-O and As-Fe bond distances indicated that As(III) forms both bidentate and monodentante corner-sharing complexes with Fe(III) octahedra. Edge-sharing As(III) complexes were less energetically favorable and had As-O and As-Fe distances that deviated more from experimentally measured values than corner-sharing complexes. The hydrated bidentate complex was the most energetically favorable in the vacuum phase, while the monodentate complex was most favored in the aqueous phase. Structures optimized using the Harris and Perdew-Wang local functionals were close to both experimental data and structures optimized using the nonlocal Becke-Lee-Yang-Parr (BLYP) functional. Binding energies calculated with the gradient-corrected BLYP functional were only weakly dependent on the method used for geometry optimization. The approach of using low-level structures coupled with higher level single-point energies was found to reduce computational time by 75% with no loss in accuracy of the computed binding energies.