Observation of resonant interatomic coulombic decay in Ne clusters.

We have measured the electron spectra of Ne clusters after excitation with photon energies around the 2s inner valence threshold. At two photon energies below threshold, a resonantly enhanced surplus of low kinetic-energy electrons is observed. The kinetic energy of the peak does not vary with the photon energy and is slightly larger than the transition energy of Interatomic Coulombic Decay (ICD) above threshold. This leads us to assume that an ICD-like process is present. In analogy to the Auger and the resonant Auger decay this new phenomenon is termed resonant ICD.

Experimental evidence for interatomic coulombic decay in Ne clusters.

Electron spectra of photoexcited Ne clusters are shown to display a signal at low kinetic energies that is neither present in the Ne monomer nor at photon energies below the inner-valence 2s threshold. These findings are strong evidence for the existence of interatomic Coulombic decays (ICD), a mechanism that was recently predicted theoretically [Phys. Rev. Lett. 79, 4778 (1997)]]. In ICD, an inner-valence hole state in a weakly bonded system can undergo ultrafast relaxation due to energy transfer to a neighboring atom, followed by electron emission from this neighboring site.

Intramolecular electron scattering and electron transfer following autoionization in dissociating molecules.

Resonant Auger decay of core-excited molecules during ultrafast dissociation leads to a Doppler shift of the emitted electrons depending on the direction of the electron emission relative to the dissociation axis. We have investigated this process by angle-resolved electron-fragment ion coincidence spectroscopy. Electron energy spectra for selected emission angles for the electron relative to the molecular axis reveal the occurrence of intermolecular electron scattering and electron transfer following the primary emission. These processes amount to approximately 25% of the resonant atomic Auger intensity emitted in the studied transition.

Femtosecond interatomic Coulombic decay in free neon clusters: large lifetime differences between surface and bulk.

A quantitative determination of 2s vacancy lifetimes in surface and bulk atoms of free Ne clusters has been made. While for free atoms the 2s inner-valence hole has a ps lifetime, it reduces to 6+/-1 fs for cluster bulk atoms. For surface atoms, the lifetime is on average longer than 30 fs. The lifetime estimate was obtained from fits of high-resolution photoelectron spectra of Ne clusters. The shortening of the lifetime is attributed to the coordination dependent interatomic Coulombic decay, which is extremely sensitive to internuclear distances.