Trapped laser-cooled atomic ions are a new tool for understanding cold molecular ions. The atomic ions not only sympathetically cool the molecular ions to millikelvin temperatures, but the bright atomic ion fluorescence can also serve as a detector of both molecular reactions and molecular spectra. We are working towards the detection of single molecular ion spectra by sympathetic heating spectroscopy. Sympathetic heating spectroscopy uses the coupled motion of two trapped ions to measure the spectra of one ion by observing changes in the fluorescence of the other ion. Sympathetic heating spectroscopy is a generalization of quantum logic spectroscopy, but does not require ions in the motional ground state or coherent control of the ion internal states. We have recently demonstrated this technique using two isotopes of Ca+ [Phys. Rev. A, 81, 043428 (2010)]. Limits of the method and potential applications for molecular spectroscopy are discussed.
This thesis presents the results of my graduate work which has concentrated on applying laser-cooling techniques to molecular ions, specifically CaH⁺ and BH⁺ ions for the study of their rovibronic spectroscopy. The goal of my research has been to control external and internal degrees of freedom of these two ions. Each of these molecules is spectroscopically appealing in its own right. For starters, CaH⁺ has been identified as a potential system for the test for the time variation of fundamental constants, and it's also been speculated to be in space. BH⁺ has a nearly diagonal Franck-Condon structure, and could be directly laser-cooled using only a few lasers. This structure makes it a good candidate for the cooling of internal molecular degrees of freedom. Each of the experiments described in this review involves the trapping and laser-cooling of ions. We cool the molecular ions sympathetically with laser-cooled Ca⁺. The probing techniques used to collect data are mainly: laser induced fluorescence, mass spectrometry, and resonance-enhanced multi-photon dissociation (REMPD). We have demonstrated the ground state sympathetic cooling of CaH⁺ ion to less than 16
muK, and we have used to REMPD to measure for the first time four vibronic transitions in CaH⁺ ions. Together, these results are important for future quantum logic experiments on this molecule. Furthermore, we have also made some progress towards trapping and cooling BH⁺ ions by first trapping B⁺ ions with Ca⁺ ions. We use the motional resonance method to detect the B⁺ ions, which can be reacted with H atoms to produce the molecular ions. Following the measurement of the vibronic spectrum of CaH⁺, we have narrowed the linewidth of the laser source to resolve rotational lines.