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Microwave Spectrum, Dipole Moment, and Internal Dynamics of the Methyl Fluoride−Carbonyl Sulfide Weakly Bound Complex

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journal contribution
posted on 21.02.2008, 00:00 by Michal M. Serafin, Sean A. Peebles
Rotational spectra for the normal and four isotopically substituted species of the 1:1 complex between methyl fluoride (H3CF) and carbonyl sulfide (OCS) have been measured using Fourier-transform microwave spectroscopy in the 5−16 GHz frequency region. The observed spectra fit well to a semirigid Watson Hamiltonian, and an analysis of the rotational constants has allowed a structure to be determined for this complex. The dipole moment vectors of the H3CF and OCS monomers are aligned approximately antiparallel with a C···C separation of 3.75(3) Å and with an ab plane of symmetry. The values of the Pcc planar moments were found to be considerably different from the expected rigid values for all isotopologues. An estimate of ∼14.5(50) cm-1 for the internal rotation barrier of the CH3 group with respect to the framework of the complex has been made using the Pcc values for the H3CF−OCS and D3CF−OCS isotopic species. Two structures, very close in energy and approximately related by a 60° rotation about the C3 axis of the methyl fluoride, were identified by ab initio calculations at the MP2/6-311++G(2d,2p) level and provide reasonable agreement with the experimental rotational constants and dipole moment components.