The Near-ultraviolet Absorption Spectrum of Diimide in Liquid Ammonia and its Decomposition between −65 and −38 °C

The near-ultraviolet absorption spectrum of diimide in liquid ammonia at −50 °C is shifted about 500 Å to the red compared with the gas-phase spectrum, with λmax = 4000 Å. The spectrum is also broadened and the vibrational structure largely obscured. It is suggested that hydrogen bonding is responsible for these changes.Diimide is much more stable in liquid ammonia between −65 and −38 °C than in the gas phase at room temperature. A first-order decay is observed with Arrhenius parameters of A = 1.9 × 103 s−1 and E = 6.6 kcal/mol; this is always preceded by a more rapid, higher-order initial decay which may be related to the rapid decomposition observed during vaporization.