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.

中文翻译：

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面内复合物的原子间库仑衰减率

Van der Waals内面体复合物中的原子间库仑衰变（ICD）异常快速。但是，可用的理论内面复合体中ICD速率的计算仅考虑平衡几何结构，其中被包封的原子位于富勒烯笼的中心。在这里我们通过分析显示，偶极等离子体激元共振对ICD的主要贡献没有偏离其平衡几何值，而对于室温下内膜状复合物的大多数原子位移，较高的多极等离子体激元对ICD的贡献可忽略不计。这与离子型内膜化合物预测的行为相反。