A theory of electronic structure for coarse-grained resolutions
We present a stochastic diabatic projection method for constructing electronic structure models that operate at coarse-grained (CG) molecular resolutions. By minimizing the relative entropy of joint electronic-nuclear distributions between the fine-grained (FG) and CG resolutions, we derive a stochastic effective Hamiltonian that decomposes CG configuration dependent electronic structure into deterministic means and residual fluctuations. This framework bridges downfolding and molecular coarse-graining theory, enabling the systematic reproduction of electronic structure renormalized over eliminated nuclear and electronic degrees of freedom.
Authors
- Nicholas E. Jackson (ORCID: https://orcid.org/0000-0002-1470-1903)
Institutions
- University of Illinois Urbana-Champaign (US)
Publication Details
- Journal
- The Journal of Chemical Physics
- Published
- 2026-07-16
- DOI
- https://doi.org/10.1063/5.0329731
- Primary Topic
- Surface Chemistry and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 0.00