Abstract

Low energy states of CaO+ have been examined by means of two-color threshold ionization spectroscopy. It is established that the ground state is X2Πi and the first excited state, just 685 cm−1 higher in energy, is A2Σ+. Due to the close proximity of the X2Π1/2 and A2Σ+ vibronic levels, they are mutually perturbing via the spin-orbit operator. A deperturbation analysis is presented for two pairs of levels. These measurements also yielded improved values for the ionization energy of CaO (55,428± 3 cm−1) and the bond dissociation energy of CaO+ (27,000± 600 cm−1). The results validate previous theoretical calculations and provide spectroscopic data of value for future ion trap studies of CaO+ at ultra-cold temperatures.

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