Quantum-classical solvation hydrodynamics: Hamiltonian functionals and dissipation

Physics > Chemical Physics Title:Quantum-classical solvation hydrodynamics: Hamiltonian functionals and dissipation View PDF HTML (experimental)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 correlated to both the position and molecular orientation coordinates of the liquid. This approach retains essential solute-solvent correlations while significantly 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. Current browse context: Bibliographic and Citation Tools Code, Data and Media Associated with this Article Demos Recommenders and Search Tools 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.