The Fourier transform microwave spectrum of 4-methylacetophenone recorded from 8 GHz to 18 GHz under jet-cooled conditions has revealed large tunneling splittings arising from a low barrier to internal rotation of the ring methyl group and small splittings from a high torsional barrier of the acetyl methyl group. The large splittings are especially challenging to model, while the small splittings are difficult to analyze due to the resolution limit of 120 kHz. The combination of two methyl groups undergoing internal rotations caused each rotational transition to split into five torsional species, which were resolved and fitted using a modified version of the XIAM code and the newly developed ntop code to a root-mean-square deviation close to measurement accuracy, providing an estimate of the V 3 potential barriers of about 22 cm −1 and 584-588 cm −1 for the ring and the acetyl methyl groups, respectively. The assignment was aided by separately fitting the five torsional species using odd-power order operators. Only one conformer in which all heavy atoms are located on a symmetry plane could be identified in the spectrum, in agreement with results from conformation analysis using quantum chemical calculations.

The flash pyrolysis of trans 3-pentenenitrile (3-PN, CH3-CH=CH-CH2-CN) was studied by combining the results of VUV photoionization mass spectra with broadband microwave spectra recorded as a function of the temperature...

We report details of the design and operation of a single apparatus that combines Chirped-Pulse Fourier Transform Microwave (CP-FTMW) spectroscopy with vacuum ultraviolet (VUV) photoionization Time-of-Flight Mass Spectrometry (TOFMS). The supersonic expansion used for cooling samples is interrogated first by passing through the region between two microwave horns capable of broadband excitation and detection in the 2-18 GHz frequency region of the microwave. After passing through this region, the expansion is skimmed to form a molecular beam, before being probed with 118 nm (10.5 eV) single-photon VUV photoionization in a linear time-of-flight mass spectrometer. The two detection schemes are powerfully complementary to one another. CP-FTMW detects all components with significant permanent dipole moments. Rotational transitions provide high-resolution structural data. VUV TOFMS provides a gentle and general method for ionizing all components of a gas phase mixture with ionization thresholds below 10.5 eV, providing their molecular formulae. The advantages, complementarity, and limitations of the combined methods are illustrated through results on two gas-phase mixtures made up of (i) three furanic compounds, two of which are structural isomers of one another, and (ii) the effluent from a flash pyrolysis source with o-guaiacol as the precursor.