Vibrational exchange upon interconversion tunneling in (HF)2 and (HCCH)2

Publisher Website
Google Scholar
Abstract
Model calculations are presented to interpret the large H–F and C–H stretching vibrational dependencies of the interconversion tunneling splittings and the corresponding infrared vibrational‐tunneling state selection rules in (HF)2 and (HCCH)2. The model consists of two potential curves in the tunneling coordinate, coupled by an interaction term that allows the vibrational excitation to be exchanged between the two monomer units, permitting tunneling to occur. The interaction term is approximated by resonant infrared transition–dipole coupling. The magnitudes of the calculated vibrational dependencies, their isotopic shifts, and the predicted selection rules are in agreement with previous experimental observations.