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The definition of the activation energy is exactly the same -- the thermodynamic energy barrier that the reactant must pass over to convert to products.

The difference between a thermal and a photochemical reaction is only where the reactants get the energy to get over this barrier. In a thermal reaction, that energy is given by the temperature, and is carried in excited rotational modes, higher kinetic energies and if hot enough, excited vibrational states. In a photochemical reaction, the activation energy is provided by photons, usually in the form of electronic excited states, but could also be vibrational or rotational. The concept of the activation barrier is identical in both cases.

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