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Context.The methyl cation (CH₃⁺) has recently been discovered in the interstellar medium through the detection of 7 μm (1400 cm⁻¹) features toward the d203-506 protoplanetary disk by the JWST. Line-by-line spectroscopic assignments of these features, however, were unsuccessful due to complex intramolecular perturbations preventing a determination of the excitation and abundance of the species in that source.

Aims.Comprehensive rovibrational assignments guided by theoretical and experimental laboratory techniques provide insight into the excitation mechanisms and chemistry of CH₃⁺in d203-506.

Methods.The rovibrational structure of CH₃⁺was studied theoretically by a combination of coupled-cluster electronic structure theory and (quasi-)variational nuclear motion calculations. Two experimental techniques were used to confirm the rovibrational structure of CH₃⁺:(1) infrared leak-out spectroscopy of the methyl cation, and (2) rotationally resolved photoelectron spectroscopy of the methyl radical (CH₃). In (1), CH₃⁺ions, produced by the electron impact dissociative ionization of methane, were injected into a 22-pole ion trap where they were probed by the pulses of infrared radiation from the FELIX free electron laser. In (2), neutral CH₃, produced by CH₃NO₂pyrolysis in a molecular beam, was probed by pulsed-field ionization zero-kinetic-energy photoelectron spectroscopy.

Results.The quantum chemical calculations performed in this study have enabled a comprehensive spectroscopic assignment of thev₂⁺andv₄⁺bands of CH₃⁺detected by the JWST. The resulting spectroscopic constants and derived EinsteinAcoefficients fully reproduce both the infrared and photoelectron spectra and permit the rotational temperature of CH₃⁺(T= 660 ± 80 K) in d203-506 to be derived. A beam-averaged column density of CH₃⁺in this protoplanetary disk is also estimated.

The planarity of the second stable conformer of 1,3‐butadiene, the archetypal diene for the Diels–Alder reaction in which a planar conjugated diene and a dienophile combine to form a ring, is not established. The most recent high level calculations predicted the species to adopt a twisted, gauche structure owing to steric interactions between the inner terminal hydrogens rather than a planar, cis structure favored by the conjugation of the double bonds. The structure cis‐1,3‐butadiene is unambiguously confirmed experimentally to indeed be gauche with a substantial dihedral angle of 34°, in excellent agreement with theory. Observation of two tunneling components indicates that the molecule undergoes facile interconversion between two equivalent enantiomeric forms. Comparison of experimentally determined structures for gauche‐ and trans‐butadiene provides an opportunity to examine the effects of conjugation and steric interactions.