Shs. Wilson et al., NEAR-THRESHOLD PHOTODISSOCIATION OF C2H2, C2HD, AND C2D2 STUDIED BY H(D) ATOM PHOTOFRAGMENT TRANSLATIONAL SPECTROSCOPY, Bulletin of the Chemical Society of Japan, 69(1), 1996, pp. 71-76
The photodissociation of jet-cooled C2H2, C2HD, and C2D2 molecules fol
lowing excitation within their respective predissociated Angstrom-X ab
sorption band systems has been investigated using the technique of H(D
) Rydberg-atom photofragment translational spectroscopy. Analyses of t
he rotational structure apparent in the resulting total kinetic-energy
release spectra yields precise values for the DCC-H, HCC-D, and DCC-D
bond dissociation energies: D-0(0)(DCC-H)=46144+/-50 cm(-1), D-0(0)(H
CC-D)=46687+/-50 cm(-1), and D-0(0)(DCC-D)=46754+/-50 cm(-1) respectiv
ely. The average internal excitation of bending vibration in the C2H(C
2D) fragments formed from these photolyses of all three parent isotopo
mers is shown to scale linearly with the excess energy over and above
that required for bond fission by ca. 540 cm(-1).