Coupled internal rotations and 14N quadrupole hyperfine structure of 2,4-dimethylpyrrole investigated by microwave spectroscopy and quantum chemistry

Abstract

The microwave spectrum of 2,4-dimethylpyrrole was investigated using a Fourier-transform microwave spectrometer in a supersonic expansion. Torsional splittings arising from two inequivalent methyl internal rotors in combination with hyperfine splittings due to the nuclear quadrupole coupling of the 14N nucleus were observed. The experiments were accompanied by quantum chemical calculations. A total of 1561 rotational lines were assigned and fitted in global fits using the programs XIAM and BELGI-Cs-2Tops-hyperfine, both achieved the measurement accuracy of 4 kHz. Local separate fits were also performed to verify the correctness of the assignment. Accurate experimental molecular and internal rotation parameters could be deduced and compared to the calculated ones. The barrier to internal rotation of the 2-methyl rotor was determined to be 277.830(26) cm−1, essentially the same as the value of about 280 cm−1 found for 2-methylpyrrole but lower than the value of 317 cm−1 found for 2,5-dimethylpyrrole. The torsional barrier value of the 4-methyl rotor is 262.210(27) cm−1, slightly higher than the value of 246 cm−1 found for 3-methylpyrrole. Benchmarking the rotational constants for 2,4- and 2,5-dimethylpyrrole revealed that the MP2/6-31G(d,p) level could be helpful to guide the assignment of microwave spectra of pyrrole derivatives.