Rotational spectra of ten new fluoroethylene/CO2 clusters, (C2H3F)x(CO2)y: Application of data-centered methods to the assignment of spectra in complex mixtures

Abstract

Chirped-pulse Fourier-transform microwave (CP-FTMW) spectroscopy has been used to measure the spectra of ten previously unobserved fluoroethylene (FE)/CO₂ clusters, (FE)_x(CO₂)_y, with x from 1 to 4 and y from 0 to 4. Multiple spectra were recorded with varying concentrations of CO₂ in the sample, and at least 400,000 free induction decays averaged per data set. This allowed implementation of data-centered approaches, using intensity variation, to identify subsets of transitions belonging to the same cluster species or those of similar composition, simplifying the assignment process for the complex mixture of clusters present. All spectra were fitted to Watson A-reduction Hamiltonians, including quartic distortion constants, with very few species requiring higher order distortion constants for satisfactory fits to be obtained. Computational data at MP2/6-311++G(2d,2p) and ωB97X-D/6-31+G(d,p) levels suggested FE:CO₂ ratios and likely structural arrangements of each cluster based on comparisons with experimental rotational constants.