Structure, energetics, and spectroscopy of the chromophores of HHe+n, H₂He+n, and He+n clusters and their deuterated isotopologues

Abstract

The linear molecular ions H2He+, HHe+2, and He+3 are the central units (chromophores) of certain He-solvated complexes of the H2He+n, HHe+n, and He+n families, respectively.

Improving potential energy surfaces using measured Feshbach resonance states

“…This compares with earlier bound state calculations using the FCI PES predicting a value of D 0 = 1784 cm −1 (19). This value was confirmed from a subsequent focal point analysis resulting in D 0 = 1789(4) cm −1 for para − H + 2 (25). Furthermore, a range of reactive collision experiments was carried out which yielded total and differential cross sections, depending on the vibrational state of the diatomic (21) but with marked differences between observed and computed results.…”

Unusual Dynamics and Vibrational Fingerprints of van der Waals Dimers Formed by Linear Molecules and Rare-Gas Atoms

“…These computations were executed at the frozen-core MP2 and CCSD­(T) levels, relying on user-defined triple- (uTZ), quadruple- (uQZ), and pentuple-zeta (u5Z) basis sets. The u X Z bases include (i) the MA X basis functions for H and He, and (ii) the aug-cc-pV X Z basis sets for the other atoms, where X = T(3), Q(4), and P(5). To avoid the nonzero force dilemma, , the (an)­harmonic force constants have been derived at the fully optimized reference structures.…”

“…In recent studies involving our group, – interesting structural, dynamical, and spectroscopic results have been reported for the HHe n + and He n + systems, whereby either a proton or a positive charge is “solvated” by He atoms, respectively. In particular, results obtained for HHe 3 + , where a He atom solvates the formally linear HHe 2 + cation, led us to the present study of the structure, dynamics, and vibrational fingerprints for a collection of van der Waals (vdW) dimers, composed of neutral or charged linear chromophores and a single rare-gas (Rg) atom, Rg = He, Ne, and Ar.…”