The global kinetic-thermodynamic relationship derived from first principles.

ABSTRACT: What governs the relationship between the reaction rate and thermodynamic driving force? Despite decades of rate theory, no general physically grounded equation exists to relate rate and driving force across all regimes. Classical models, such as the Marcus equation and Leffler equations, either rely on under-realistic assumptions or only capture the local behaviour, failing outside narrow regimes. We derive a general, non-linear equation from microscopic reversibility, arriving at three physically meaningful parameters: a minimum preorganisational barrier (E _min), a reaction symmetry offset (E _eq), and a kinetic curvature factor (θ). This model captures global behaviour, recovers known limits, and explains why classical models like Leffler equati

SUBMITTER: Garcia-Padilla E 

PROVIDER: S-EPMC12406046 | biostudies-literature | 2025 Aug

REPOSITORIES: biostudies-literature