Theoretical determination of the ionization potentials of CaF, SrF, and BaF
Aleksandra A. Kyuberis, Lukáš F. Pašteka, Ephraim Eliav, H. A. Perrett, Ayaki Sunaga, Silviu‐Marian Udrescu, S. G. Wilkins, R. F. García Ruíz, Anastasia Borschevsky
Abstract
We present a comprehensive theoretical study of the ionization potentials of the $M\mathrm{F}$ $(M=\mathrm{Ca}, \mathrm{Sr}, \mathrm{and} \mathrm{Ba})$ molecules using the state-of-the-art relativistic coupled-cluster approach with single, double, and perturbative triple excitations [CCSD(T)]. We have further corrected our results for higher-order excitations (up to full triples) and the QED self-energy and vacuum-polarization contributions. We have performed an extensive investigation of the effect of the various computational parameters on the calculated ionization potentials, which allowed us to assign realistic uncertainties to our predictions. For CaF and BaF, where precise experimental measurements are available, our predictions are in excellent agreement with the measured values. In the case of SrF, we provide a theoretical prediction of the ionization potential that deviates from the available experimental measurements, motivating further experimental investigations.