Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways
Open accessAbstract
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.
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Later studies revealed inaccuracies in calculating reaction energies in the vacuum approach resulting from the omission of electric field and solvation effects during the simulation.
“However, later studies revealed inaccuracies in calculating reaction energies in this approach.[34-37][38] resulting from the omission of electric field and solvation effects during the simulation.”
From Electrochemical CO <sub>2</sub> Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design (2019) · cites this paper as [37]
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- Authors
- Mathew, K., Sundararaman, R., Letchworth-Weaver, K., Arias, T. A., & Hennig, R. G.
- Affiliations
- Cornell University (US)
- Cornell University 2 Department of Physics, , Ithaca, New York 14853, USA
- Venue
- The Journal of Chemical Physics
- Publisher
- AIP Publishing
- Published
- 2014-02-26
- Volume
- 140
- Issue
- 8
- Pages
- 084106-084106
- ISSN
- 0021-9606 (ISSN-L)
- 1089-7690
- OpenAlex
- W2115234257
- Cited by
- 3,196
- References
- 39
- Citations by year
- 2026: 511 · 2025: 587 · 2024: 469 · 2023: 408 · 2022: 356 · 2021: 280 · 2020: 220 · 2019: 136 · 2018: 110 · 2017: 53 · 2016: 43 · 2015: 18 · 2014: 5
- FWCI
- 19.72
- Type
- journal article
- Language
- en
- Open access
- green
- arxiv.org
- Locations
- The Journal of Chemical Physics (publishedVersion)
- PubMed (publishedVersion)
- arXiv (Cornell University) (submittedVersion)
- OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
- arXiv (Cornell University)
- Funders
- DOE (DE-SC0001086)
- Topics
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Advanced Chemical Physics Studies
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Advanced Physical and Chemical Molecular Interactions
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Spectroscopy and Quantum Chemical Studies
- Keywords
- implicit solvation models, solid-liquid interface, nanocrystal surfaces, surface energy, semiconducting nanocrystals, metal nanocrystals, reaction barriers, solvent effects
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