Molecular beam photoelectron spectroscopy and femtosecond intramolecular dynamics of H2O+ and D2O+

Autor:	Yuan-Pern Lee, D. A. Shirley, J. E. Reutt, Lai-Sheng Wang
Rok vydání:	1986
Předmět:	Chemistry Relaxation (NMR) Born–Oppenheimer approximation General Physics and Astronomy Electronic structure Photoionization Ion symbols.namesake X-ray photoelectron spectroscopy Correlation function symbols Physical and Theoretical Chemistry Atomic physics Molecular beam
Zdroj:	The Journal of Chemical Physics. 85:6928-6939
ISSN:	1089-7690 0021-9606
DOI:	10.1063/1.451379
Popis:	The 584 A 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.
Databáze:	OpenAIRE
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