The tetrahydrofuran...hydrogen chloride complex: Rotational spectrum and theoretical analysis

摘要

The hydrogen bonded heterodimer tetrahydrofuran...HCl has been investigated using molecular beam Fourier transform microwave spectroscopy in combination with ab initio calculations. The rotational spectrum, observed in the range 6-18 GHz, shows a complex pattern originated by the existence of small tunneling splittings in addition to the Cl-nuclear quadrupole coupling hyperfine structure. The vibrational energy difference between the members of the doublet, #DELTA#E = 3.550(25) MHz, has been determined from the analysis of the a-type Coriolis coupling interaction between them. Doublets of the same magnitude are also present in the spectra of the different HCl isotopomers analyzed. These tunneling splittings were not observed for the species C_4D_8O...H~(35)Cl. The analysis of all the available data has allowed us to conclude that these splittings are due to pseudorotation within the tetrahydrofuran subunit. The spectroscopic constants have been interpreted in terms of a geometry in which tetrahydrofuran has a conformation close to the twisted ring-form with HCl lying on the plane bisector to the COC ring angle. The potential energy surface for the interaction between tetrahydrofuran and hydrogen chloride has been explored by using ab initio methodologies at the correlated level [MP2, MP4(SDTQ)] with Pople's 6-31G~(**) and Dunning's aug-cc-pVDZ basis sets. One minimum and three transition structures were located and characterized at the MP2/6-31G** level. The geometry parameters and rotational constants of the minimum agree quite well with those determined from the spectroscopic data. The transition structures correspond to interconversions between equivalent conformations, the first one via an inversion motion and the remaining two via pseudorotation movements. One of these latter two is responsible for the splittings detected in the microwave spectroscopy study. The tetrahydrofuran...hydrogen chloride interaction can be seen as a combination of electrostatic and charge transfer contributions both consistent with the angular geometry exhibited by the complex.