Interplay between charge and vibrational delocalization in cationic helium clusters

The stable structures and low temperature thermodynamics of cationic helium clusters are investigated theoretically using a diatomics-in-molecules model for the potential energy surfaces and a computational framework in which both electronic and nuclear degrees of freedom are treated on a quantum mechanical footing. While the charge is generally carried by two atoms, vibrational delocalization significantly spreads out the charge over multiple isomers for clusters containing five or more helium atoms. Our calculations indicate that large clusters are essentially fluid with a well-defined solvation shell around the charged core.