title: Cationic noble gas hydrides: a theoretical investigation of dinuclear HNgFNgH+ (Ng = He-Xe).
abstract: Theoretical calculations at the B3LYP, MP2, and CCSD(T) levels of theory disclose the conceivable existence of cationic noble gas hydrides containing two Ng atoms. These species have a general formula of HNgFNgH(+) (Ng = He-Xe), and are the cationic counterparts of the neutral HNgF. The optimized geometries, harmonic frequencies, and bonding properties point to ion-dipole complexes between a fluoride anion and two covalent H-Ng(+) cations, best formulated as (H-Ng(+))(2)F(-). The HXeFXeH(+) is also isoelectronic with the recently experimentally observed HXeOXeH (Khriachtchev et al. J. Am. Chem. Soc. 2008, 130, 6114-6118). The resulting HNgFNgH(+) are thermochemically stable with respect to dissociation into HNg(+) + HNgF and HNg(+) + H + Ng + F, but are largely unstable with respect to both the loss of HF (with formation of HNg(+) + Ng) and H(2)F(+) (with formation of two Ng atoms). These decompositions pass through bent transition structures, and only the heaviest HArFArH(+), HKrFKrH(+), and HXeFXeH(+) are protected by energy barriers large enough (ca. 10-15 kcal mol(-1)) to support their conceivable metastability. In line with other series of noble gas compounds, the neon cation HNeFNeH(+) is the least stable among the various HNgFNgH(+).
authors.affiliation: Dipartimento di Scienze Ambientali, Università della Tuscia, L.go dell' Università, s.n.c., 01100 Viterbo, Italy.
authors.forename: Stefano
authors.initials: S
authors.lastname: Borocci
authors.forename: Nicoletta
authors.initials: N
authors.lastname: Bronzolino
authors.forename: Maria
authors.initials: M
authors.lastname: Giordani
authors.forename: Felice
authors.initials: F
authors.lastname: Grandinetti