The smallest proton-bound dimer H 5 + : theoretical progress

• Published in: Philosophical transactions of the Royal Society of London. Series A: Mathematical, physical, and engineering sciences physical, and engineering sciences, 2019-09, Vol.377 (2154), p.20180396
• Main Authors: Prosmiti, Rita, Valdés, Álvaro
• Format: Article
• Language: English
• ISSN: 1364-503X; 1471-2962
• DOI: 10.1098/rsta.2018.0396

The protonated hydrogen dimer, H , is the smallest system including proton transfer, and has been of long-standing interest since its first laboratory observation in 1962. H and its isotopologues are the intermediate complexes in deuterium fractionation reactions, and are of central importance in molecular astrophysics. The recently recorded infrared spectra of both H and D reveal a rich vibrational dynamics of the cations, which presents a challenge for standard theoretical approaches. Although H is a four-electron ion, which makes highly accurate electronic structure calculations tractable, the construction of ab initio-based potential energy and dipole moment surfaces has proved a hard task. In the same vein, the difficulties in treating the nuclear motion could also become cumbersome due to their high dimensionality, floppiness and/or symmetry. These systems are prototypical examples for studying large-amplitude motions, as they are highly delocalized, interconverting between equivalent minima through internal rotation and proton transfer motions requiring state-of-the-art treatments. Recent advances in the computational vibrational spectroscopy of the H cation and its isotopologues are reported from full quantum spectral simulations, providing important information in a rigorous manner, and open perspectives for further future investigations. This article is part of a discussion meeting issue 'Advances in hydrogen molecular ions: H , H and beyond'.