In contrast to a [4 + 2] cycloaddition, a [2 + 2] cycloaddition does not occur under thermal conditions,
but does take place photochemically. This result is explained by examining the symmetry
of the HOMO and LUMO of the alkene reactants.
In a thermal [2 + 2] cycloaddition, like phases of the p orbitals on only one set of terminal carbons
can overlap. For like phases to overlap on the other terminal carbon, the molecule must
twist to allow for an antarafacial pathway. This process cannot occur to form small rings.