Interatomic coulombic decay rate in endohedral complexes

Abstract

Abstract Interatomic coulombic decay (ICD) in van der Waals endohedral complexes was predicted to be anomalously fast. However, the available theoretical calculations of the ICD rates in endohedral complexes only consider the equilibrium geometry, in which the encapsulated atom is located at the centre of the fullerene cage. Here we show analytically that the dominant contribution of the dipole plasmon resonance to ICD does not deviate from its equilibrium geometry value, while contributions of higher multipole plasmons to the ICD can be neglected for most atomic displacements possible for an endohedral complex at room temperature. This is in contrast to the behaviour predicted for ionic endohedral compounds. Our results show that the conclusion of the earlier works on the ultrafast character of the ICD in endohedral complexes holds generally for a wide range of geometries possible under a thermal distribution, rather than only for the equilibrium geometry.