ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
The 584 A(ring) photoelectron spectra of supersonic molecular beams of H2O and D2O have been obtained with improved resolution. The spectroscopic constants of the X˜ 2B1 and A˜ 2A1 state ions, including ω01, x011, ω02, x022, and x012, are reported. For the first two electronic states of the ion, precise line splittings were evaluated with a least squares fitting procedure, employing sums of empirical instrument response functions and a linear background. A simulation of the vibrational manifolds of the B˜ 2B2 state ions with combination progressions in the symmetry-allowed modes ν1 and ν2 failed to reproduce the diffuse photoelectron bands observed for both H2O and D2O. Autocorrelation functions were calculated from the photoelectron bands of all three electronic states. The B˜ 2B2 state correlation functions exhibit ultrafast decay, occurring on a 10−14 s time scale. The ν2 motion appears to define the decay in the correlation function. This behavior supports a previously proposed B˜ 2B2–A˜ 2A1 curve-crossing model for the nonradiative relaxation of the B˜ 2B2 state ions.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.451379
