The Influence of a Changing Local Environment during Photoinduced CO 2 Dissociation

Though largely influencing the efficiency of a reaction, molecular-scale details local environment reactants are experimentally inaccessible hindering an in-depth understanding catalyst's reactivity, prerequisite to maximizing its efficiency. We introduce method follow individual molecules and their changing during photochemical reaction. The is illustrated for rate-limiting step in photolytic dissociation CO2 on two catalytically relevant surfaces, Ag(100) Cu(111). reveal with single-molecule resolution how reactant's surroundings evolve progressing laser illumination it propensity dissociation. Counteracting processes lead volcano-like reactivity. Our unprecedented view photoinduced reaction opens avenue influence products yields nanoscale.