Vibrational frequencies and stark tuning rate with continuum electro-chemical models and grand canonical density functional theory

[2509.10307] Vibrational frequencies and stark tuning rate with continuum electro-chemical models and grand canonical density functional theory Skip to main content Search Submit Donate Log in Physics > Chemical Physics arXiv:2509.10307 (physics) [Submitted on 12 Sep 2025 ( v1 ), last revised 9 Feb 2026 (this version, v2)] Title: Vibrational frequencies and stark tuning rate with continuum electro-chemical models and grand canonical density functional theory Authors: Mouyi Weng , Nicéphore Bonnet , Oliviero Andreussi , Nicola Marzari View PDF HTML (experimental) Abstract: Simulating electrochemical interfaces using density functional theory (DFT) requires incorporating the effects of electrochemical potential. The electrochemical potential acts as a new degree of freedom that can effectively tune DFT results as electrochemistry does. Typically, this is implemented by adjusting the number of electrons on the solid surface within the Kohn-Sham (KS) equation, under the framework of an implicit solvent model and the Poisson-Boltzmann equation (PB equation), thereby modulating the potential difference between the solid and liquid. These simulations are often referred to as grand-canonical or fixed-potential DFT calculations. To apply this additional degree of freedom, Legendre transforms are employed in the calculation of free energy, establishing the relationship between the grand potential and the free energy. Other key physical properties, such as atomic forces, vibrational frequencies, and Stark tuning rates, can be derived based on this relationship rather than directly using Legendre transforms. This paper begins by discussing the numerical methodologies for the continuum model of electrolyte double layers and grand-potential algorithms. We then show that atomic forces under grand-canonical ensemble match the Hellmann-Feynman forces observed in canonical ensemble, as previously established. However, vibrational frequencies and Stark tuning rates exhibit distinct behaviors between these conditions. Through finite displacement methods, we confirm that vibrational frequencies and Stark tuning rates exhibit differences between grand-canonical and canonical ensembles. Subjects: Chemical Physics (physics.chem-ph) Cite as: arXiv:2509.10307 [physics.chem-ph] (or arXiv:2509.10307v2 [physics.chem-ph] for this version) https://doi.org/10.48550/arXiv.2509.10307 Focus to learn more arXiv-issued DOI via DataCite Journal reference: npj Computational Materials (2026) Related DOI : https://doi.org/10.1038/s41524-026-02200-z Focus to learn more DOI(s) linking to related resources Submission history From: Mouyi Weng [ view email ] [v1] Fri, 12 Sep 2025 14:49:22 UTC (694 KB) [v2] Mon, 9 Feb 2026 13:34:49 UTC (685 KB) Full-text links: Access Paper: View PDF HTML (experimental) TeX Source view license Current browse context: physics.chem-ph < prev | next > new | recent | 2025-09 Change to browse by: physics References & Citations SciX Google Scholar Semantic Scholar export BibTeX citation Bookmark Bibliographic Tools Bibliographic and Citation Tools Bibliographic Explorer Toggle Bibliographic Explorer ( What is the Explorer? ) Connected Papers Toggle Connected Papers ( What is Connected Papers? ) Litmaps Toggle Litmaps ( What is Litmaps? ) scite.ai Toggle scite Smart Citations ( What are Smart Citations? ) Code, Data, Media Code, Data and Media Associated with this Article alphaXiv Toggle alphaXiv ( What is alphaXiv? ) Links to Code Toggle CatalyzeX Code Finder for Papers ( What is CatalyzeX? ) DagsHub Toggle DagsHub ( What is DagsHub? ) GotitPub Toggle Gotit.pub ( What is GotitPub? ) Huggingface Toggle Hugging Face ( What is Huggingface? ) ScienceCast Toggle ScienceCast ( What is ScienceCast? ) Demos Demos Replicate Toggle Replicate ( What is Replicate? ) Spaces Toggle Hugging Face Spaces ( What is Spaces? ) Spaces Toggle TXYZ.AI ( What is TXYZ.AI? ) Related Papers Recommenders and Search Tools Link to Influence Flower Influence Flower ( What are Influence Flowers? ) Core recommender toggle CORE Recommender ( What is CORE? ) Author Venue Institution Topic About arXivLabs arXivLabs: experimental projects with community collaborators arXivLabs is a framework that allows collaborators to develop and share new arXiv features directly on our website. Both individuals and organizations that work with arXivLabs have embraced and accepted our values of openness, community, excellence, and user data privacy. arXiv is committed to these values and only works with partners that adhere to them. Have an idea for a project that will add value for arXiv's community? Learn more about arXivLabs . Which authors of this paper are endorsers? | Disable MathJax ( What is MathJax? ) We gratefully acknowledge support from our major funders , member institutions , and all contributors. About · Help · Contact · Subscribe · Copyright · Privacy · Accessibility · Operational Status (opens in new tab)

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