The pyrrole-water complex: Multidimensional large amplitude dynamics and rotational spectra of its 13C isotopologues

Abstract

The rotational spectrum of pyrrole-water was investigated before (Tubergen et al., 1993) In this work, we have applied a recently developed semiempirical tight-binding quantum chemistry program and DFT calculations to identify possible low energy conformers of the pyrrole-water complex which feature σ- and π-type hydrogen-bonding interactions. Using a cavity-based and two chirped pulse Fourier transform microwave spectrometers, we have measured and assigned all monosubstituted 13C isotopologues of pyrrole-water in their natural abundances. The 14N nuclear quadrupole hyperfine splittings and water tunneling doublets of these rarer isotopologues have also been observed and analyzed. Furthermore, we have carried out potential energy surface scans along possible paths of water large amplitude motions and identified all four previously proposed pyrrole-water geometries and correlated them to one global minimum and three transition states. The theoretical investigation together with the additional 13C experimental data allow one to confidently identify the ground state geometry and also estimate the water tunneling barrier.