Abstract
Implicit solvent models are a computationally efficient method of representing solid/liquid interfaces prevalent in electrocatalysis, energy storage, and materials science. However, electronic structure changes induced at the metallic surface by the dielectric continuum are not fully understood. To address this, we perform DFT calculations for the Pt(111)/water interface, in order to compare Poisson-Boltzmann continuum solvation methods with ab initio molecular dynamics (AIMD) simulations of explicit solvent. We show that the implicit solvent cavity can be parametrized in terms of the electric dipole moment change at the equilibrated explicit Pt/water interface to obtain the potential of zero charge (PZC). We also compare the accuracy of aqueous enthalpies of adsorption of phenol on Pt(111) using geometry and charge density based dielectric cavitation methods. The ability to parametrize the cavity according to individual atoms, as afforded in the geometry based approach, is key to obtaining accurate enthalpy changes of adsorption under aqueous conditions. We also show that the electronic structure changes induced by explicit solvent and our proposed implicit solvent parametrization scheme yield comparable density difference profiles and d-band projected density of states. We therefore demonstrate the capability of implicit solvent approaches to capture both the energetics of adsorption processes and the main electronic effects of aqueous solvent on the metallic surface. This work therefore provides a scheme for computationally efficient simulations of interfacial processes for applications in areas such as heterogeneous catalysis and electrochemistry.
| Original language | English |
|---|---|
| Pages (from-to) | 2703-2715 |
| Number of pages | 13 |
| Journal | Journal of Chemical Theory and Computation |
| Volume | 16 |
| Issue number | 4 |
| DOIs | |
| State | Published - Apr 14 2020 |
| Externally published | Yes |
Funding
G.B. (partial support), V.-A.G., M.-T.N., and R.R. were supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemistry, Geochemistry and Biological Sciences, and located at Pacific Northwest National Laboratory (PNNL). Computational resources were provided by National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility located at Lawrence Berkeley National Laboratory (LBNL). PNNL is operated by Battelle for the US Department of Energy under Contract DE-AC05-76RL01830. Computational resources were provided by PNNL Research Computing and the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility supported by the Office of Science of the U.S. DOE, located at Lawrence Berkeley national lab (LBNL). G.B. acknowledges the EPSRC for partial support in PhD funding. The authors acknowledge the use of the IRIDIS High Performance Computing Facility (IRIDIS 5) and associated support services at the University of Southampton in the completion of this work. We are grateful to the UK Materials and Molecular Modelling Hub (Thomas HPC) for computational resources, which is partially funded by EPSRC (EP/P020194/1).
| Funders | Funder number |
|---|---|
| Division of Chemistry, Geochemistry and Biological Sciences | |
| UK Materials and Molecular Modelling Hub | EP/P020194/1 |
| U.S. Department of Energy | DE-AC05-76RL01830 |
| Office of Science | |
| Basic Energy Sciences | |
| Lawrence Berkeley National Laboratory | |
| Pacific Northwest National Laboratory | |
| Engineering and Physical Sciences Research Council |