Nature of the molecule-surface encounter Adsorption is an important initial step in all heterogeneous chemical processes. However, detailed adsorption dynamics are complex and challenging to follow experimentally. Using the fact that vibrationally excited carbon monoxide molecules can be trapped on the Au(111) surface with all degrees of freedom being equilibrated except the vibrational ones, Borodin et al. show that the vibrational relaxation time can serve as an internal clock to follow the microscopic pathways of adsorption and equilibration on the surface. On the basis of molecular beam experiments and theoretical modeling of this prototypical system, the authors reveal the intricate interplay between physisorption and chemisorption states. These observed characteristics are relevant to many other heterogeneous systems. Science , this issue p. 1461 Vibrational relaxation time of CO can serve as an internal clock to follow the pathways of its adsorption on Au(111). Adsorption involves molecules colliding at the surface of a solid and losing their incidence energy by traversing a dynamical pathway to equilibrium. The interactions responsible for energy loss generally include both chemical bond formation (chemisorption) and nonbonding interactions (physisorption). In this work, we present experiments that revealed a quantitative energy landscape and the microscopic pathways underlying a molecule’s equilibration with a surface in a prototypical system: CO adsorption on Au(111). Although the minimum energy state was physisorbed, initial capture of the gas-phase molecule, dosed with an energetic molecular beam, was into a metastable chemisorption state. Subsequent thermal decay of the chemisorbed state led molecules to the physisorption minimum. We found, through detailed balance, that thermal adsorption into both binding states was important at all temperatures.