Abstract
We have examined the titled dissociation reaction near its 0 K threshold using 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 CD 4 exhibits a sharp step at the 0 K threshold, indicating that the dissociation of excited CD 4 in high- n ( n⩾100) Rydberg states at energies above the dissociation threshold occurs in ⩽10 −7 s. The energetic data for CD 3/ CD 3 + and CD 4/ CD 4 + are found to be in excellent agreement with those for CH 3/ CH 3 + and CH 4/ CH 4 + after taking into account the zero-point-vibrational-energy corrections.
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