Duality between relaxation and first passage in reversible Markov dynamics: rugged energy landscapes disentangled

Relaxation and first passage processes are the pillars of kinetics in condensed matter, polymeric and single-molecule systems. Yet, an explicit connection between relaxation and first passage time-scales so far remained elusive. Here we prove a duality between them in the form of an interlacing of spectra. In the basic form the duality holds for reversible Markov processes to effectively one-dimensional targets. The exploration of a triple-well potential is analyzed to demonstrate how the duality allows for an intuitive understanding of first passage trajectories in terms of relaxational eigenmodes. More generally, we provide a comprehensive explanation of the full statistics of reactive trajectories in rugged potentials, incl. the so-called 'few-encounter limit'. Our results are required for explaining quantitatively the occurrence of diseases triggered by protein misfolding. (fast track communication)