Exploring photoionization of gas-phase free radicals with a widely tunable VUV laser at moderate spectral resolution

The VUv Laser for Considering Astrophysical and Isolated Molecules (VULCAIMs) setup [Harper et al., Phys. Chem. Chem. Phys. 24, 2777 (2022)] integrates a narrow-bandwidth tunable vacuum ultraviolet (VUV) and extreme ultraviolet (XUV) nanosecond-pulsed laser system (6–16 eV) and a photoelectron spectrometer, designed for recording high-spectral-resolution (rotationally resolved) photoelectron spectra of gas-phase free radicals. This approach usually needs beforehand medium-resolution synchrotron data to guide the selection of specific spectral regions to be investigated at higher resolution with the VULCAIM setup. We present an upgraded version of the VUV laser system integrating an optical parametric oscillator for continuously scanned medium-resolution measurements (<3 cm−1) across the whole VUV and XUV spectral ranges. This innovation enables broader coverage without the need to access synchrotron facilities. Furthermore, rapid mode switching allows for maintaining optimized radical production conditions from mid-resolution to high-resolution operation mode, enhancing spectroscopy capabilities significantly. The new capabilities of the VULCAIM setup are illustrated on two showcases of photoionization studies: the nitric oxide (NO) stable molecular species and the benzyl (C6H5CH2) free radical produced by pyrolysis.