H/D substitution makes difference in photochemical studies: the case of dimethylamine

When the molecule in the excited state is subject to prompt predissociation, it is quite nontrivial to obtain vibrational structure of the excited state in general. This applies to the case of photochemistry of dimethylamine (DMA:$(CH_3)_2NH$). When DMA is excited to its first electronically excited state ($S_1$), the N-H bond dissociation occurs promptly. Therefore, $S_1$ vibronic bands are homogeneously broadened to give extremely small ionization cross sections and heavily-congested spectral features, making infeasible any reasonable spectral assignment. Here, we demonstrate that the predissociation rate of the excited state could be significantly reduced by the NH/ND substitution to give the much better-resolved $S_1$ spectral feature, revealing the vibrational structure of the excited state of $DMA-d_1$ ($(CH_3)_2ND$) for the first time.