In the case of photochemical reactions, light provides the activation energy. Simplistically, light is one mechanism for providing the activation energy required for many reactions. If laser light is employed, it is possible to selectively excite a molecule so as to produce a desired electronic and vibrational state. Equally, the emission from a particular state may be selectively monitored, providing a measure of the population of that state. If the chemical system is at low pressure, this enables scientists to observe the energy distribution of the products of a chemical reaction before the differences in energy have been smeared out and averaged by repeated collisions.
The absorption of a photon by a reactant molecule may also permit a reaction to occur not just by bringing the molecule to the necessary activation energy, but also by changing the symmetry of the molecule's electronic configuration, enabling an otherwise-inaccessible reaction path, as described by the Woodward–Hoffmann selection rules. A [2+2] cycloaddition reaction is one example of a pericyclic reaction that can be analyzed using these rules or by the related frontier molecular orbital theory.
Some photochemical reactions are several orders of magnitude faster than thermal reactions; reactions as fast as 10 seconds and associated processes as fast as 10 seconds are often observed.
The photon can be absorbed directly by the reactant or by a photosensitizer, which absorbs the photon and transfers the energy to the reactant. The opposite process, when a photoexcited state is deactivated by a chemical reagent, is called quenching.
Most photochemical transformations occur through a series of simple steps known as primary photochemical processes. One common example of these processes is the excited state proton transfer.