Solvation of cationic copper clusters in molecular hydrogen

Multiply charged superfluid helium nanodroplets are utilized to facilitate the growth of cationic copper clusters (Cu n + , where n = 18) that are subsequently solvated with up to 50 H 2 molecules. Production of both pristine and protonated cationic Cu clusters are detected mass spectrometrically. A joint effort between experiment and theory allows us to understand the nature of the interactions determining the bonding between pristine and protonated Cu + and Cu 2 + cations and molecular hydrogen. The analysis reveals that in all investigated cationic clusters, the primary solvation shell predominantly exhibits a covalent bonding character, which gradually decreases in strength, while for the subsequent shells an exclusive non-covalent behaviour is found. Interestingly, the calculated evaporation energies associated with the first solvation shell markedly surpass thermal values, positioning them within the desirable range for hydrogen storage applications. This comprehensive study not only provides insights into the solvation of pristine and protonated cationic Cu clusters but also sheds light on their unique bonding properties. We underscore a solid agreement between experimental and computational studies on solvation of pristine/protonated Cu n + ( n = 12) in H 2 . For instance, with n = 1, the initial shell comprises four covalently bound H 2 ; subsequent ones are non-covalent.