A theoretical study on the infrared signatures of proton-bound rare gas dimers (Rg-H + -Rg), Rg = {Ne, Ar, Kr, and Xe}

Abstract

The infrared spectrum of proton-bound rare gas dimers has been extensively studied via matrix isolation spectroscopy. However, little attention has been paid on their spectrum in the gas phase. Most of the Rg 2 H + has not been detected outside the matrix environment. Recently, Ar n H + (n = 3-7) has been first detected in the gas-phase [D. C. McDonald et al., J. Chem. Phys. 145, 231101 (2016)]. In that work, anharmonic theory can reproduce the observed vibrational structure. In this paper, we extend the existing theory to examine the vibrational signatures of Rg 2 H + , Rg = {Ne, Ar, Kr, and Xe}. The successive binding of Rg to H + was investigated through the calculation of stepwise formation energies. It was found that this binding is anti-cooperative. High-level full-dimensional potential energy surfaces at the CCSD(T)/aug-cc-pVQZ//MP2/aug-cc-pVQZ were constructed and used in the anharmonic calculation via discrete variable representation. We found that the potential coupling between the symmetric and asymmetric Rg-H + stretch (ν 1 and ν 3 respectively) causes a series of bright n 1 ν 1 + ν 3 progressions. From Ne 2 H + to Xe 2 H + , an enhancement of intensities for these bands was observed.