Nonstatistical Photoinduced Processes in Gaseous Organic Molecules

Processes that proceed in femtoseconds are usually referred to as being ultrafast, and they are investigated in experiments that involve laser pulses with femtosecond duration in so-called pump probe schemes, where a light pulse triggers a molecular process and a second light pulse interrogates the temporal evolution of the molecular population. The focus of this review is on the reactivity patterns that arise when energy is not equally distributed on all the available degrees of freedom as a consequence of the very short time scale in play and on how the localization of internal energy in a specific mode can be thought of as directing a process toward (or away from) a certain outcome. The nonstatistical aspects are illustrated with examples from photophysics and photochemistry for a range of organic molecules. The processes are initiated by a variety of nuclear motions that are all governed by the energy gradients in the Franck–Condon region. Essentially, the molecules will start to adapt to the new electronic environment on the excited state to eventually reach the equilibrium structure. It is this structural change that is enabling an ultrafast electronic transition in cases where the nuclear motion leads to a transition point with significant coupling between to electronic states and to ultrafast reaction if there is a coupling to a reactive mode at the transition point between the involved states. With the knowledge of the relation between electronic excitation and equilibrium structure, it is possible to predict how the nuclei move after excitation and often whether an ultrafast (and inherently nonstatistical) electronic transition or even a bond breakage will take place. In addition to the understanding of how nonstatistical photoinduced processes proceed from a given excited state, it has been found that randomization of the energy does not even always take place when the molecule takes part in processes that are normally considered statistical, such as for example nonradiative transitions between excited states. This means that energy can be localized in a specific degree of freedom on a state other than the one that is initially prepared. This is a finding that could kickoff the ultimate dream in applied photochemistry; namely light excitation that leads to the rupture of a specific bond.