The conformational stability of gaseous 1-butene studied by femtosecond nonlinear spectroscopy and ab initio calculations

1-Butene was investigated by rotational femtosecond degenerate four-wave mixing spectroscopy (fs DFWM) under supersonic expansion conditions as well as by quantum chemical calculations. Fs DFWM is a time-resolved rotational Raman spectroscopy, which allows for precise determination of rotational constants. The experimental fs DFWM spectrum was successfully reproduced by a fitted simulation using a single structure ascribed to the gauche conformer of 1-butene. The obtained rotational constants A = 22.6 ± 1.7 GHz, B = 4.1554 ± 0.0004 GHz and C = 4.0550 ± 0.0004 GHz are in excellent agreement with the ones from microwave spectroscopy. The cis conformer was not observed in the fs DFWM spectrum recorded under the low-temperature conditions of a supersonic expansion. The absence of the cis form along with simulations of a fs DFWM spectrum indicate that the cis conformer is at most equally but most likely less stable than the gauche rotamer. The experimental findings were supplemented by high level quantum chemical calculations, which predict the gauche form to have lower total energy than the cis structure.