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MO: Molekülphysik

MO VII: HV VII

MO VII.1: Hauptvortrag

Freitag, 8. März 2002, 11:00–11:40, HS 01/E01

Electronic Decay of Valence Holes in Clusters — •Robin Santra, Jürgen Zobeley, and Lorenz S. Cederbaum — Theoretische Chemie, Physikalisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg

Electronically excited cations, generated by inner-valence ionization of small molecules, relax in general by dissociation and, eventually, photon emission. Typically, autoionization is forbidden for energetic reasons. Using extensive ab initio calculations, we have shown that the situation changes fundamentally in an inner-valence ionized cluster, which releases its excess energy by emitting an electron. This novel process, referred to as Intermolecular Coulombic Decay, is characterized by an efficient Coulombic energy transfer mechanism between monomers in the cluster. The decay phenomenon is ultrafast, taking place on a femtosecond timescale. The electronic emission is accompanied by interesting dynamical effects amenable to experimental observations. These effects arise as a consequence of the weak chemical bond in clusters and the Coulomb repulsion pattern in the final-state dication.

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