Deuterium Isotope Effect in the Radiative Triplet Decay of Heavy Atom Substituted Aromatic Molecules

We studied the effect of deuteration on the radiative decay of the triplet sublevels of naphthalene and some halogenated derivatives. We found that the influence of deuteration is much more pronounced in the heavy atom substituted than in the parent hydrocarbons. The strongest change upon deuteration is in the radiative decay of the out-of-plane polarized spin state Tx. These findings are consistently related to a second order Herzberg-Teller (HT) spin-orbit coupling. Though we found only a small influence of deuteration on the total radiative rate in naphthalene, a significantly larger effect is observed in the rate of the 00-transition of the phosphorescence. This result is discussed in terms of a change of the overlap integral of the vibrational groundstates of Tx and S0 upon deuteration.