Unveiling distinct bonding patterns in noble gas hydrides via interference energy analysis †

Despite their apparent simplicity, the helium hydride ion (HeH+) and its analogues with heavier noble gas (Ng) atoms present intriguing challenges due to their unusual electronic structures and distinct ground-state heterolytic bond dissociation profiles. In this work, we employ modern valence bond calculations and the interference energy analysis to investigate the nature of the chemical bond in NgH+ (Ng = He, Ne, Ar). Our findings reveal that the energy well formation in their ground-state potential energy curves is driven by a reduction in kinetic energy caused by quantum interference, identical to cases of homolytic bond dissociation. However, clear differences in bonding situation emerge: in HeH+ and ArH+, electron charge transfer leads to Ng+–H covalent bonds, while in NeH+, a preferred Ne + H+ valence bond structure suggests the formation of a dative bond. This study highlights the distinct bonding mechanisms within the NgH+ series, showcasing the interplay between quantum interference and quasi-classical effects in molecules featuring noble gases.