The outcome of neutral and photoionized N(CH3)(2) primary products of trimethylamine photodissociation at 193 nm is determined by combining photoionization detection with supporting G3 theoretical calculations. N(CH3)(2) primary products with very little internal energy show an experimentally observed ionization onset of 9.1 +/- 0.2 eV, but do not appear at the parent ion (m/e = 44). Instead, the parent ion is unstable and easily fragments to m/e = 42, where the signal is observed. N(CH3)(2) radicals with higher internal energies undergo H-atom loss from the neutral to give CH2NCH3, which has an observed ionization onset at parent (m/e = 43) of < 9.3 eV. At slightly higher ionization energies, these secondary products also appear at m/e = 42 (where their appearance energy is roughly 9.8-9.9 eV, uncorrected for internal energy). Finally, N(CH3)(2) radicals with the highest internal energy in this study appear to undergo H-2 loss as neutrals, giving rise to a species whose parent ion has m/e = 42. The ionization onset of this species at m/e = 42 is found to be in the range of 9.5-9.6 eV.