title: Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways.
abstract: Solid-liquid interfaces are at the heart of many modern-day technologies and provide a challenge to many materials simulation methods. A realistic first-principles computational study of such systems entails the inclusion of solvent effects. In this work, we implement an implicit solvation model that has a firm theoretical foundation into the widely used density-functional code Vienna ab initio Software Package. The implicit solvation model follows the framework of joint density functional theory. We describe the framework, our algorithm and implementation, and benchmarks for small molecular systems. We apply the solvation model to study the surface energies of different facets of semiconducting and metallic nanocrystals and the SN2 reaction pathway. We find that solvation reduces the surface energies of the nanocrystals, especially for the semiconducting ones and increases the energy barrier of the SN2 reaction.
authors.affiliation: Department of Materials Science and Engineering, Cornell University, Ithaca, New York 14853, USA.
authors.forename: Kiran
authors.initials: K
authors.lastname: Mathew
authors.affiliation: Department of Physics, Cornell University, Ithaca, New York 14853, USA.
authors.forename: Ravishankar
authors.initials: R
authors.lastname: Sundararaman
authors.affiliation: Department of Physics, Cornell University, Ithaca, New York 14853, USA.
authors.forename: Kendra
authors.initials: K
authors.lastname: Letchworth-Weaver
authors.affiliation: Department of Physics, Cornell University, Ithaca, New York 14853, USA.
authors.forename: T A
authors.initials: TA
authors.lastname: Arias
authors.affiliation: Department of Materials Science and Engineering, Cornell University, Ithaca, New York 14853, USA.
authors.forename: Richard G
authors.initials: RG
authors.lastname: Hennig