Spectroscopy, lifetime, and charge-displacement of the methanol-noble gas complexes: An integrated experimental-theoretical investigation

Abstract

An integrated experimental-theoretical investigation was employed to determine rovibrational energies, spectroscopic constants, lifetime as a function of temperature in gas phase complexes of methanol with noble gas (NgHe, Ne, Ar, Kr, Xe, and Rn). Beside that, a parallel effort has been addressed to theoretically characterize the nature of intermolecular interactions determining the dissociation energy and equilibrium distance of the formed adducts. Dynamics and lifetime results reveal that, except for the CH3OH-He aggregate, all other methanol-Ng compounds are sufficiently stable under thermal conditions. Their lifetimes are larger than 1ps for the temperature of the bulk in the range between 200 and 500K. In addition, the current lifetime results suggest that the aggregates formed by methanol and Ng are globally more stable than corresponding complexes formed by water with Ng. From the point of view of the CCSD(T)/aug-cc-pVTZ level calculation, in all compounds, the electron densities of Ng partners are weakly polarized in the presence of CH3OH molecule. The charge-displacement curves and NBO analysis indicate that the charge transfer from Ng to methanol molecule, in general, plays a minor role, being appreciable only in the aggregate involving Ar. Finally, it was verified from the SAPT2+(CCD)-δMP2/aug-cc-pVTZ calculations and NCI analysis that the dispersion is the essential long-range attractive contribution to the interaction energy for all studied complexes. This feature strongly suggests that these compounds are held bonded substantially by van der Waals forces. Then non-covalent intermolecular bonds are effectively formed in the gas phase, which is disturbed by small stabilizing charge-transfer contributions.