My understanding of exothermic reactions is that, in the aggregate, the sum of the bond energies of the products is lower than that of the reactants, and definitely lower than that of the sum of any excited state intermediates, and that the resulting difference in energy is accounted for by a decrease in potential energy for the bonding electrons involved, resulting in a release of photons of equivalent energy.
Seeing as how exothermic reactions generally raise the temperature of the environment they are in, it seems logical to me that those photons are rapidly absorbed (inelastically) by atoms/molecules immediately neighboring the reaction products and thus their kinetic energies are raised, although I honestly don't truly understand the mechanism for that, either.
Similarly, for reactions that are isothermal but which are chemiluminescent, photons of a wavelength not easily absorbed by neighboring atoms/molecules simply leave the environment.
However, does that mean that the inverse is true? Is IR radiation from the environment the direct mediator of energy transfer that raises bonding electrons in reactants to anti-bonding MOs so that new MOs can form among different configurations of the original reactant atoms, thus allowing electrons to occupy the bonding MOs of the products?
I ask because the basic collision theory proposed by Trautz and Lewis doesn't seem to account for quantum mechanical models of energy, but I admit my own understanding of the topic is about as limited as my question would demonstrate.