The photoexcitation of a thermal polyatomic molecule at room temperature from a ground electronic state to an excited one is accompanied by a nonequilibrium distribution of the internal energy in the excited state. The nature of the excited state distribution - whether hot or cold - may be controlled through the photoexcitation frequency. The nascent distribution may have a profound effect on unimolecular isomerization, internal conversion or electron transfer rates in the excited state. These rates may be controlled through the frequency and temporal properties of the photoexcitation pulse. Conversely, measurement of the rates serves as a molecular thermometer for the nascent distribution in the excited electronic state. Examples to be discussed are recent experiments on the stilbene system, model electron transfer reactions, benzene and naphthalene. The recent criticism by Troe and coworkers of our interpretationof the dynamics of the stilbene system will also be addressed.