Abstract
Abstract Autoionization is an important pathway for the relaxation of electronically excited states. In weakly bonded matter, efficient autoionization channels have been found, in which not only the initially excited state, but also neighbouring atoms or molecules take part. Since their theoretical prediction in 1997 these processes are known as interatomic or intermolecular coulombic decay (ICD). The author summarizes the experimental research on ICD up to the presence. Experiments on inner valence ICD in rare gas clusters, on cascade ICD after Auger decay and on ICD of satellite states are explicitly discussed. First experiments on water clusters and on solutes will be reviewed. An outlook on other non-local autoionization processes and on future directions of ICD research closes the article.
Highlights
A vacancy site in an isolated atom or molecule can relax by floures3 cence, dissociation or—if energy permits—by autoionization
Efficient autoionization channels have been found, in which the initially excited state, and neighbouring atoms or molecules take part. Since their theoretical prediction in 1997 these processes are known as Interatomic or Intermolecular Coulombic Decay (ICD)
In the case of weak bonding, e.g. by hydrogen bridges or dispersion 9 forces, it is possible to discuss the electronic structure in terms of the one of 10 the isolated system
Summary
A vacancy site in an isolated atom or molecule can relax by floures cence, dissociation or—if energy permits—by autoionization. It has long been known that the double ionization threshold of clus ters is lower with respect to the monomer [1] This is natural, as in a cluster two hole states can have the vacancies located at different sites, resulting in a Coulomb repulsion energy which is lower than in the isolated system. |kε describes an electron of low kinetic energy, that is of large wavelength It is for this reason that the matrix element (2) may connect the two orbitals |ov , |ov′ at different site effectively. |ov , |ov′ the rate drops ∼ R−6, characteristic of a dipole-dipole coupling This is a remarkable property of ICD, as most energy and charge transfer processes known today have an exponential dependence on distance. This view has enabled a most fascinating view on ICD: Using a formalism for the propagation of the correlated hole density in a quantum system, the authors of ref. [17] showed a time-dependent picture of the filling of a Ne 2s vacancy from a 2p orbital in NeAr, and the synchronous creation of an Ar 3p vacancy and a continuum electron
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