Quantum-classical solvation hydrodynamics: a Hamiltonian modeling framework

Abstract:We propose a mixed quantum-classical hydrodynamic framework to model short-time inertial effects in the non-adiabatic evolution of a quantum solute coupled to a classical polar solvent. Drawing upon the work of Burghardt and Bagchi [Chem. Phys. 329 (2006), 343], we employ the Hamiltonian approach to incorporate consistent backreaction and preserve quantum decoherence beyond standard Ehrenfest dynamics. The solvent is treated as an ideal polar fluid and the quantum solute state is coupled to both the position and molecular orientation coordinates of the liquid. This approach retains essential solute-solvent correlations while reducing the computational complexity of previous approaches. We further incorporate dissipative terms to capture both inertial effects and polarization relaxation. After establishing the general setting for non-local dielectric continua, the Marcus local approximation is integrated into the model thereby extending traditional solvation theory to account for collective fluid sloshing on fast timescales.

35 pages, two appendices. Revised manuscript. Comments welcome

Chemical Physics (physics.chem-ph); Computational Physics (physics.comp-ph); Fluid Dynamics (physics.flu-dyn); Quantum Physics (quant-ph)

arXiv:2605.05658 [physics.chem-ph]

(or arXiv:2605.05658v3 [physics.chem-ph] for this version)

https://doi.org/10.48550/arXiv.2605.05658 Focus to learn more arXiv-issued DOI via DataCite

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.