Autodetachment spectroscopy and dynamics of dipole bound states of negative ions: 2A1–2B1 transitions of H2CCC-

Yokoyama, K.; Leach, Gary W.; Kim, Joseph B.; Lineberger, W. C.
December 1996
Journal of Chemical Physics;12/22/1996, Vol. 105 Issue 24, p10696
Academic Journal
The H[SUB2]CCC[SUP-] ion is studied by autodetachment spectroscopy in a coaxial laser-ion beam spectrometer. Sharp resonances at photon energies near the photodetachment threshold energy are ascribed to a [SUP2]A[SUB1] ← [SUP2]B[SUB1] transition followed by autodetachment of the dipole-bound state (DBS). Some 2500 rotational transitions are assigned and the band origin is determined to be 14 284.420(5) cm[SUP-1]. The observation of individual rotational lines allowed determination of the rotational spectroscopic constants as A59.651 53(4) cm[SUP-1] and (B + C)/2 = 0.346 461(3) cm[SUP-1] for the DBS as well as the spin-rotation coupling constant ∊[SUBaa] = 2.17(6) × 10 cm[SUP-3] cm cm[SUP-1]. Based on an electron affinity of 14 469 ± 64 cm[SUP-1], the binding energy of the electron in the DBS is 170 ± 50 cm[SUP-1]. Anomalous rotational line positions are found in the vicinity of K[SUBa] = 7-10 in the DBS and have been attributed to the centrifugal distortion couplings caused by mixing with the CCC out-of-plane bending mode (ν[SUB6]) and the CCC in-plane bending mode (ν[SUB9]). The linewidths provide information about autodetachment rates that make it possible to obtain electron detachment dynamics for individual rotational states.


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