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Here, we describe our pulsed helium droplet apparatus for spectroscopy of molecular ions. Our approach involves the doping of the droplets of about 10 nm in diameter with precursor molecules, such as ethylene, followed by electron impact ionization. Droplets containing ions are irradiated by the pulsed infrared laser beam. Vibrational excitation of the embedded cations leads to the evaporation of the helium atoms in the droplets and the release of the free ions, which are detected by the quadrupole mass spectrometer. In this work, we upgraded the experimental setup by introducing an octupole RF collision cell downstream from the electron impact ionizer. The implementation of the RF ion guide increases the transmission efficiency of the ions. Filling the collision cell with additional He gas leads to a decrease in the droplet size, enhancing sensitivity to the laser excitation. We show that the spectroscopic signal depends linearly on the laser pulse energy, and the number of ions generated per laser pulse is about 100 times greater than in our previous experiments. These improvements facilitate faster and more reproducible measurements of the spectra, yielding a handy laboratory technique for the spectroscopic study of diverse molecular ions and ionic clusters at low temperature (0.4 K) in He droplets. [ABSTRACT FROM AUTHOR]

The methanium CH 5 + is a prototypical fluxional ion whose infrared spectra remain unassigned. Here we report on the infrared spectra of CH 5 + cations and its deuterated isotopomer, CH 4 D + , in helium droplets at a low temperature of 0.38 K. The ions were produced upon protonation of CH 4 molecules, a technique that was developed in this work. The spectra of CH 5 + around 3000 cm -1 show two strong and broad infrared bands and a weak shoulder, reflecting its highly fluxional nature. The spectrum of CH 4 D + shows a much sharper infrared band, indicating a partial quenching of the exchange of H/D atoms. This work also reports on the infrared spectrum of the methane dimer radical cations (CH 4 ) 2 + .