Dopant ionization and efficiency of ion and electron ejection from helium nanodroplets

Photoionization spectroscopy and mass spectrometry of doped helium (He) nanodroplets rely on the ability to efficiently detect ions and/or electrons. Using a commercial quadrupole mass spectrometer and a photoelectron-photoion coincidence (PEPICO) spectrometer, we systematically measure yields of ions and electrons created in pure and doped He nanodroplets in a wide size range and in two ionization regimes – direct ionization and secondary ionization after resonant photoexcitation of the droplets. For two different types of dopants (oxygen molecules, O${}_2$, and lithium atoms, Li), we infer the optimal droplet size to maximize the yield of ejected ions. When dopants are ionized by charge-transfer to photoionized He nanodroplets, the highest yield of O${}_2$ and Li ions is detected for a mean size of $\sim 5\times {10}^4$ He atoms per nanodroplet. When dopants are Penning ionized via photoexcitation of the He droplets, the highest yield of O${}_2$ and Li ions is detected for $\sim {10}^3$ and $\sim {10}^5$ He atoms per droplet, respectively. At optimum droplet sizes, the detection efficiency of dopant ions in proportion to the number of primary photoabsorption events is up to 20,% for charge-transfer ionization of O${}_2$ and 2,% for Li, whereas for Penning ionization it is 1,% for O${}_2$ and 4,% for Li. Our results are instrumental in determining optimal conditions for mass spectrometric studies and photoionization spectroscopy of molecules and complexes isolated in He nanodroplets.