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A unimolecular reaction isn't about collision, but more about a rearrangement of the molecule. For example, decomposition or radioactive decay can occur of a single molecule without any collisions occurring simply because the molecule is breaking apart/rearranging itself into multiple molecules.
Molecularity refers to the number of species in an elementary step. In a unimolecular reaction, there is only one species in the elementary step. The reaction can be unimolecular if there is a rearrangement of a single molecule that produces product.
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