A pulsed field ionization study of the dissociative photoionization reaction CD4+hv -> CD3++D+e(-)

We have examined the titled dissociation reaction near its 0 K threshold us ing the pulsed field ionization-photoelectron (PFI-PE) and PFI-PE-photoion coincidence methods. This study yields a value of 14.4184 +/- 0.0010 eV for the 0 K threshold. The PFI-PE spectrum for CD4 exhibits a sharp step at th e 0 K threshold, indicating that the dissociation of excited CD4 in high-n (n greater than or equal to 100) Rydberg states at energies above the disso ciation threshold occurs in less than or equal to 10(-7) s. The energetic d ata for CD3/C-3(+) and CD4/CD4+ are found to be in excellent agreement with those for CH3/CH3- and CH4/CH4+ after taking into account the zero-point-v ibrational-energy corrections. (C) 2001 Published by Elsevier Science B.V.