Physics & Astronomy Faculty Publications and Presentations
Document Type
Article
Publication Date
8-2024
Abstract
The high-resolution rotational spectrum of chlorosulfonic acid (ClSO2OH) has been studied using both broadband and cavity-based Fourier transform microwave spectrometers over the frequency range of 5–18 GHz. a-, b-, and c-type transitions have been recorded for both the 35Cl and 37Cl isotopologues. The observation of c-type lines establishes that the molecule lacks a plane of symmetry and suggests that the OH group can undergo large amplitude motion between equivalent structures. Interconversion between these structures can be achieved via internal rotation through two inequivalent barriers occurring at Cl-S-O-H torsional angles of 0 or 180 degrees. As in previous work on triflic and methanesulfonic acids, two states are observed and are treated as tunneling states which are presumed to arise primarily due to motion through the lower of the two barriers. The a- and c-type transitions occur within each of these states while the b-type transitions cross between them. Rotational, centrifugal distortion, and chlorine nuclear quadrupole coupling constants, as well as the energy difference between the two tunneling states and associated coupling constants, have been determined. The experimental tunneling energies, ΔE, for the 35Cl and 37Cl isotopologues are 52.6926(16) MHz and 52.6397(46) MHz, respectively. Quantum chemical calculations were carried out using MP2 and B3LYP density functional theory (DFT) methods with an aug-cc-pVTZ basis set. The rotational constants from the optimized structures were in good agreement with the experimental values. The lowest energy barrier for OH motion was calculated to be 2.63 kcal/mol at the B3LYP/aug-cc-pVTZ level. The effects of the large amplitude motion are similar to those recently reported for triflic acid (CF3SO2OH) and methanesulfonic acid (CH3SO2OH). However, while the tunneling splittings in chlorosulfonic and triflic acids are virtually identical, they differ significantly from that of methanesulfonic acid.
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Publication Title
Journal of Molecular Spectroscopy
DOI
10.1016/j.jms.2024.111927
Comments
Original published version available at https://doi.org/10.1016/j.jms.2024.111927