Joint density-functional theory for electronic structure of solvated systems

S. A. Petrosyan, Jean-Francois Briere, David Roundy, and T. A. Arias
Phys. Rev. B 75, 205105 – Published 8 May 2007

Abstract

We introduce a form of density-functional theory for the ab initio description of electronic systems in contact with a molecular liquid environment. This theory rigorously joins an electron density functional for the electrons of a solute with a classical density-functional theory for the liquid into a single variational principle for the free energy of the combined system. We then present an approximate functional in which orientational ordering appears only through a simple model dielectric response. Even with the shortcomings of this preliminary functional, the resulting theory predicts, without any fitting of parameters to solvation data, solvation energies as well as state-of-the-art quantum-chemical cavity approaches, which do require such fitting. Future work should focus on including orientational ordering in the joint density functional.

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  • Received 9 February 2007

DOI:https://doi.org/10.1103/PhysRevB.75.205105

©2007 American Physical Society

Authors & Affiliations

S. A. Petrosyan, Jean-Francois Briere, David Roundy, and T. A. Arias

  • Laboratory of Atomic and Solid State Physics, Cornell University, Ithaca, New York 14853, USA

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Issue

Vol. 75, Iss. 20 — 15 May 2007

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