In a unimolecular reaction, a single molecule rearranges atoms, forming different molecules. This is illustrated by the equation
where  refers to chemical product(s). The reaction or reaction step is an isomerization if there is only one product molecule, or a dissociation if there is more than one product molecule.
In either case, the rate of the reaction or step is described by the first order rate law
where  is the concentration of species A,  is time, and  is the reaction rate constant.
As can be deduced from the rate law equation, the number of A molecules that decay is proportional to the number of A molecules available. An example of a unimolecular reaction, is the isomerization of cyclopropane to propene:
Unimolecular reactions can be explained by the Lindemann-Hinshelwood mechanism.