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

• Published in: Journal of chemical theory and computation 2023-12, Vol.19 (23), p.8767-8781
• Main Authors: Tóbiás, Roland, Simkó, Irén, Császár, Attila G.
• Format: Article
• Language: English
• Subjects: Atomic structure; Carbon dioxide; Chromophores; Dimers; Molecular structure; Potential energy; Rare gases; Spectroscopy and Excited States; T shape; Triatomic molecules; Vibrational states
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.3c00914

Detailed structural, dynamical, and vibrational analyses have been performed for systems composed of linear triatomic molecules solvated by a single rare-gas atom, He, Ne, or Ar. Among the chromophores of these van der Waals (vdW) dimers, there are four neutral molecules (CO2, CS2, N2O, and OCS) and six molecular cations (HHe2 +, HNe2 +, HAr2 +, HHeNe+, HHeAr+, and HNeAr+), both of apolar and polar nature. Following the exploration of bonding preferences, high-level four-dimensional (4D) potential energy surfaces (PESs) have been developed for 24 vdW dimers, keeping the two intramonomer bond lengths fixed. For these 24 complexes, over 1500 bound vibrational states have been obtained via quasi-variational nuclear-motion computations, employing exact kinetic-energy operators together with the accurate 4D PESs and their 2D/3D cuts. The reduced-dimensional (2D to 4D) dimer models have been compared with full-dimensional (6D) ones in the cases of the neutral CO2·Ar and charged HHe2 +·He dimers, corroborating the high accuracy of the 2D to 4D vibrational energies. The reduced-dimensional models suggest that (a) while the equilibrium structures are T-shaped and planar, the effective ground-state structures are nonplanar, (b) certain bound states belong to collinear molecular structures, even when they are not minima, (c) the vdW vibrations are heavily mixed and many states have amplitudes corresponding to both the T-shaped and collinear structures, (d) there are a few dimers, for which even some of the vdW fundamentals lie above the first dissociation limit, and (e) the vdW vibrations are almost fully decoupled from the intramonomer bending motion.