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type:text, The resonant Auger spectrum from the decay of F 1s-excited CF4 is measured. Several lines exhibit a nondispersive kinetic energy as the exciting photon energy is tuned through the resonance region. The F 1s[–1] atomiclike Auger line is split into two components due to the emission of Auger electrons by a fragment in motion, when electron emission is observed along the polarization vector of the light. This Doppler splitting is direct evidence that the core excitation leads to Td→C3v symmetry lowering, by elongation of a specific C-F bond preferentially aligned along the polarization vector of the incident photon.

type:text, The vibrational structure of the O1s[-1]2b2 core-excited state of H2O is observed and ascribed to the mixture of symmetric stretching and bending motions with a1 symmetry. The formation of H2+ is found to increase linearly with an increase in energy stored in the nuclear motion of the O1s[-1]2b2 state, demonstrating that this dissociation channel is mediated by the nuclear motion in the core-excited state. The reaction pathway to the H2+ formation along the Auger final state of H2O+, mediated by the nuclear motion before the Auger decay, is discussed with the help of ab initio potential surfaces of the Auger final states.

The vibrational structure of the O1s[-1]2b2 core-excited state of H2O is observed and ascribed to the mixture of symmetric stretching and bending motions with a1 symmetry. The formation of H2+ is found to increase linearly with an increase in energy stored in the nuclear motion of the O1s[-1]2b2 state, demonstrating that this dissociation channel is mediated by the nuclear motion in the core-excited state. The reaction pathway to the H2+ formation along the Auger final state of H2O+, mediated by the nuclear motion before the Auger decay, is discussed with the help of ab initio potential surfaces of the Auger final states.

The resonant Auger spectrum from the decay of F 1s-excited CF4 is measured. Several lines exhibit a nondispersive kinetic energy as the exciting photon energy is tuned through the resonance region. The F 1s[–1] atomiclike Auger line is split into two components due to the emission of Auger electrons by a fragment in motion, when electron emission is observed along the polarization vector of the light. This Doppler splitting is direct evidence that the core excitation leads to Td→C3v symmetry lowering, by elongation of a specific C-F bond preferentially aligned along the polarization vector of the incident photon.