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Schematic energy level diagram of the triple-resonance scheme for excitation of the stretch in with subsequent laser-induced fluorescence (LIF) detection of fragments. Molecules in long-lived or bound states near the dissociation threshold may absorb an additional photon (P3a) from the third excitation laser with subsequent dissociation on the repulsive electronically-excited state surface.
Photofragment excitation spectrum of water transitions from the second intermediate state, prepared via the following pathway: . The states are labeled by total energy, three vibrational quantum numbers and the three rotational quantum numbers , , , respectively. Vibrational labeling of the second intermediate state is only indicative.
Sample photofragment spectra of water around the onset of the absorption continuum as a function of the total rovibrational energy of . For (c)–(f) the total energy is reduced by to account for the energy of the detected fragments. The delay between the dissociation (P3) and the detection (P4) photons is in (a), (b), (d)–(f), and in (c). The dots represent the experimental data; the lines represent smoothed spectra after numerical deconvolution of the lineshape of the third excitation laser. The upper terminal levels have been reached from second intermediate states by the following transitions: (a) ; (b) ; (c) ; (d) (e) ; (f) .7 The terminal states are labeled by allowed quantum numbers, and the intermediate states are labeled by the total rovibrational energy and by the rotational quantum number .
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