Transition state theory (TST) provides a simple interpretation of many thermally
activated processes. It applies successfully on timescales and length scales that
differ several orders of magnitude: to chemical reactions, breaking of chemical
bonds, unfolding of proteins and RNA structures and polymers crossing entropic
barriers. Here we apply TST to out-of-equilibrium transport through confined
environments: the thermally activated translocation of single DNA molecules over an
entropic barrier helped by an external force field. Reaction pathways are
effectively one dimensional and so long that they are observable in a microscope.
Reaction rates are so slow that transitions are recorded on video. We find sharp
transition states that are independent of the applied force, similar to chemical
bond rupture, as well as transition states that change location on the reaction
pathway with the strength of the applied force. The states of equilibrium and
transition are separated by micrometres as compared with angstroms/nanometres for
chemical bonds.