Nonaqueous Solvent Adsorption on Transition Metal Surfaces with Density Functional Theory: Interaction of N,N-Dimethylformamide (DMF), Tetrahydrofuran (THF), and Dimethyl Sulfoxide (DMSO) with Ag, Cu, Pt, Rh, and Re Surfaces

Interfaces between solvents and transition metals play a critical role in many catalytic and electrochemical systems. In this work, we use density functional theory (DFT) to study the interactions between several common nonaqueous solvents and a number of transition metal surfaces. We investigate trends in binding energies among the metals, and the influence of specific surface sites and facets. We examine the electrostatic field dependence of the most stable binding configurations, and shed light on experimentally observed field-dependent or potential-dependent adsorption structures. We demonstrate that the reorientation of DMSO on noble metal surfaces can occur with only a relatively small change in the surface dipole moment; this result is simultaneously consistent with experimental evidence for field-dependent reorientation and measurements of surprisingly low differential capacitance of DMSO on noble metals. These results contribute to understanding competitive adsorption effects in catalysis, and also have implications for fundamental surface properties such as the surface structure, solvated work function, and potential of zero charge.