Erratum: Laser double resonance measurements of vibrational energy transfer rates and mechanisms in HF(v=2) [J. Chem. Phys. 77, 3974 (1982)]

Dissociation Dynamics of Oriented DF−HF and HF−DF Complexes: Evidence for Direct and Indirect Dissociation

“…From the combination of bolometer microcalorimetry (comparing the energy content of the two fragments as determined by the relative bolometer signals) and the energetics implied by the angular distributions, we have shown that the small angle portion of these distributions is entirely due to channels corresponding to j HF ) 11. The fact that the ratios of the sum of the DF to HF internal plus surface sticking energies are approximately the same for the (2,11), (1,11), and (0,11) channels (namely, 0.351, 0.341, and 0.335, respectively) explains why the ratios of the intensities of the first and second peaks are the same on the HF and DF sides of the angular distribution. Given that the ratio of the HF to DF signals is approximately constant for all corresponding angles, we conclude that the additional structure at larger angles must be due to channels with similar ratios to those given above.…”

“…The heights of the vertical bars in Figure 4 give the probabilities for the various channels. It is interesting to note that the probabilities for the (2,11) and (3,10) channels are rather similar even though the intensities of the corresponding peaks are very different, the latter being much weaker. This can be understood by considering that the higher kinetic energy associated with the (3,10) channel results in scattering into a larger solid angle compared with (2,11).…”

“…In fact, the only channel that is consistent with the microcalorimetry and lies at the correct energy for the peak at 8°is (0,11). Although the (1,11) channel must be between (2,11) and (0,11), there is no obvious peak in the angular distributions. As we will see, dissociation into (1,11) is not favored, for reasons that are not at all obvious.…”

“…It is a fortunate coincidence that this state lies between two widely separated fragment states, since to bring another channel to the correct recoil energy, the dissociation energy would have to be changed by a large amount (approximately 40 cm -1 ), which is well outside the anticipated error. Thus, the assignment of the (2,11) channel as the first open channel is unique. As expected from the magnitudes of the DF versus HF signals, this channel corresponds to a low j DF fragment and an HF in high j.…”

“…The hydrogen fluoride dimer is somewhat of a prototype system for the study of hydrogen bonding and vibrational dynamics. Prior to the detailed work on the dimer, numerous studies were reported on collisions between HF molecules, [1][2][3][4] which also provided important information concerning the relevant interactions. The spectroscopy of the dimer began with work in the microwave, [5][6][7][8] which provided insights into both the structure and the tunneling dynamics.…”