The rotational spectrum of the hydrogen bond heterodimer 2,5-dihydrofuran⋯HF has been investigated in the frequency region 6–18.5 GHz using molecular beam Fourier transform microwave spectroscopy. The R-branch μa-type spectra of the parent, 2,5-dihydrofuran⋯DF, Cα13-2,5-dihydrofuran⋯HF and Cβ13-2,5-dihydrofuran⋯HF species have been measured. All the observed lines are split into two components due to the tunneling of HF between the two equivalent hydrogen bonding sites at the oxygen atom. A value for the barrier to HF inversion of 100 cm−1 has been calculated from the analysis of the rotational constants of both tunneling states on the basis of a simple one-dimensional model. Ab initio calculations at the MP2/6-311+G(d,p) and MP2/6-311+G(2df,p) levels of theory have been carried out to complement the experimental data. The results on the HF inversion barrier and hydrogen bond angular geometry of 2,5-dihydrofuran⋯HF have been compared to those previously obtained for the H2O⋯HF complex.

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