Communication: electron transfer mediated decay enabled by spin-orbit interaction in small krypton/xenon clusters.
In this work we study the influence of relativistic effects, in particular spin-orbit coupling, on electronic decay processes in KrXe2 clusters of various geometries. For the first time it is shown that inclusion of spin-orbit coupling has decisive influence on the accessibility of a specific decay pathway in these clusters. The radiationless relaxation process is initiated by a Kr 4s ionization followed by an electron transfer from xenon to krypton and a final second ionization of the system. We demonstrate the existence of competing electronic decay pathways depending in a subtle way on the geometry and level of theory. For our calculations a fully relativistic framework was employed where omission of spin-orbit coupling leads to closing of two decay pathways. These findings stress the relevance of an adequate relativistic description for clusters with heavy elements and their fragmentation dynamics.
Physikalisch-Chemisches Institut, Theoretische Chemie, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany.
J Patrick
JP
Zobel
Physikalisch-Chemisches Institut, Theoretische Chemie, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany.
Nikolai V
NV
Kryzhevoi
Physikalisch-Chemisches Institut, Theoretische Chemie, Universität Heidelberg, Im Neuenheimer Feld 229, D-69120 Heidelberg, Germany.
Markus
M
Pernpointner