Quantum chemical calculations to determine partitioning coefficients for HgCl2 on iron-oxide aerosols

Highlights: • Partitioning coefficient measurements for transport models are time-consuming. • Computational chemistry can efficiently estimate partitioning coefficients. • Developed computational protocol to calculate HgCl₂ partitioning coefficients • Showed agreement between calculations and experiments for HgCl₂ on NaCl aerosols • Predicted partitioning coefficients for HgCl₂ on iron-oxide aerosol surfaces Gas-to-particle phase partitioning controls the pathways for oxidized mercury deposition from the atmosphere to the Earth's surface. The propensity of oxidized mercury species to transition between these two phases is described by the partitioning coefficient (K_p). Experimental measurements of K_p values for HgCl₂ in the presence of atmospheric aerosols are difficult and time-consuming. Quantum chemical calculations, therefore, offer a promising opportunity to efficiently estimate partitioning coefficients for HgCl₂ on relevant aerosols. In this study, density functional theory (DFT) calculations are used to predict K_p values for HgCl₂ on relevant iron-oxide surfaces. The model is first verified using a NaCl(100) surface, showing good agreement between the calculated (2.8) and experimental (29–43) dimensionless partitioning coefficients at room temperature. Then, the methodology is applied to six atmospherically relevant terminations of α-Fe₂O₃(0001): OH-Fe-R, (OH)₃-Fe-R, (OH)₃-R, O-Fe-R, Fe-O₃-R, and O₃-R (where R denotes bulk ordering). The OH-Fe-R termination is predicted to be the most stable under typical atmospheric conditions, and on this surface termination, a dimensionless HgCl₂ K_p value of 5.2 × 10³ at 295 K indicates a strong preference for the particle phase. This work demonstrates DFT as a promising approach to obtain partitioning coefficients, which can lead to improved models for the transport of mercury, as well as for other atmospheric pollutant species, through and between the anthroposphere and troposphere.