A cusp criterion for a local phase-space bottleneck in a minimal adiabatic Marcus Hamiltonian

Abstract

Marcus--Hush theory describes electron transfer through reorganization energies, driving forces, and electronic coupling, but it does not by itself determine when an adiabatic model possesses a local Hamiltonian bottleneck. We study a minimal asymmetric two-degree-of-freedom lower-sheet Hamiltonian with an exactly separable harmonic transverse mode. For this conservative model, we establish a necessary-and-sufficient root count for the stationary points and recover the known cusp boundary for disappearance of the lower-sheet double well. We then interpret that boundary in Hamiltonian phase space: inside the cusp, the lower sheet has an index-one saddle and the associated local transition-state structures --- an unstable periodic-orbit NHIM, its stable and unstable manifolds, and an attached dividing surface --- exist; outside the cusp, this local saddle-mediated structure is absent. The result applies to this conservative adiabatic potential-energy Hamiltonian. It does not describe solvent free-energy dynamics, bath-induced mode coupling, or nonadiabatic transfer, and it does not predict Marcus rates for realistic condensed-phase electron-transfer systems.

arXiv comment25 pages, 7 figures. Author accepted manuscript; title and abstract updated following peer review; exposition, references and reproducibility details revised. Published in Chemical Physics