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The potential energy landscape (PEL) formalism is a tool within statistical mechanics that has been used in the past to calculate the equation of states (EOS) of classical rigid model liquids at low temperatures, where computer simulations may be challenging. In this work, we use classical molecular dynamics (MD) simulations and the PEL formalism to calculate the EOS of the flexible q-TIP4P/F water model. This model exhibits a liquid–liquid critical point (LLCP) in the supercooled regime, at (Pc = 150 MPa, Tc = 190 K, and ρc = 1.04 g/cm3) [using the reaction field technique]. The PEL-EOS of q-TIP4P/F water and the corresponding location of the LLCP are in very good agreement with the MD simulations. We show that the PEL of q-TIP4P/F water is Gaussian, which allows us to calculate the configurational entropy of the system, Sconf. The Sconf of q-TIP4P/F water is surprisingly similar to that reported previously for rigid water models, suggesting that intramolecular flexibility does not necessarily add roughness to the PEL. We also show that the Adam–Gibbs relation, which relates the diffusion coefficient D with Sconf, holds for the flexible q-TIP4P/F water model. Overall, our results indicate that the PEL formalism can be used to study molecular systems that include molecular flexibility, the common case in standard force fields. This is not trivial since the introduction of large bending/stretching mode frequencies is problematic in classical statistical mechanics. For example, as shown previously, we find that such high frequencies lead to unphysical (negative) entropy for q-TIP4P/F water when using classical statistical mechanics (yet, the PEL formalism can be applied successfully).
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This content will become publicly available on May 21, 2026
Maximum entropy inference of reaction–diffusion models
Reaction–diffusion equations are commonly used to model a diverse array of complex systems, including biological, chemical, and physical processes. Typically, these models are phenomenological, requiring the fitting of parameters to experimental data. In the present work, we introduce a novel formalism to construct reaction–diffusion models that is grounded in the principle of maximum entropy. This new formalism aims to incorporate various types of experimental data, including ensemble currents, distributions at different points in time, or moments of such. To this end, we expand the framework of Schrödinger bridges and maximum caliber problems to nonlinear interacting systems. We illustrate the usefulness of the proposed approach by modeling the evolution of (i) a morphogen across the fin of a zebrafish and (ii) the population of two varieties of toads in Poland, so as to match the experimental data.
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- Award ID(s):
- 2347357
- PAR ID:
- 10600773
- Publisher / Repository:
- The Journal of Chemical Physics
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 162
- Issue:
- 19
- ISSN:
- 0021-9606
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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