Calcium monohydroxide radical (CaOH) is receiving an increasing amount of attention from the astrophysics community as it is expected to be present in the atmospheres of hot rocky super-Earth exoplanets as well as interstellar and circumstellar environments. Here, we report the high-resolution laboratory absorption spectroscopy on low-J transitions in A ˜ 2 Π ( 0 , 0 , 0 ) − X ˜ 2 Σ + ( 0 , 0 , 0 ) band of buffer-gas-cooled CaOH. In total, 40 transitions out of the low-J states were assigned, including 27 transitions that have not been reported in previous literature. The determined rotational constants for both ground and excited states are in excellent agreement with previous literature, and the measurement uncertainty for the absolute transition frequencies was improved by more than a factor of 3. This will aid future interstellar, circumstellar, and atmospheric identifications of CaOH. The buffer-gas-cooling method employed here is a particularly powerful method to probe low-J transitions and is easily applicable to other astrophysical molecules.

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For over five decades, studies in the field of chemical physics and physical chemistry have primarily aimed to understand the quantum properties of molecules. However, high-resolution rovibronic spectroscopy has been limited to relatively small and simple systems because translationally and rotationally cold samples have not been prepared in sufficiently large quantities for large and complex systems. In this study, we present high-resolution rovibronic spectroscopy results for large gas-phase molecules, namely, free-base phthalocya-nine (FBPc). The findings suggest that buffer-gas cooling may be effective for large molecules introduced via laser ablation. High-resolution electronic spectroscopy, combined with other experimental and theoretical studies, will be useful in understanding the quantum properties of molecules. These findings also serve as a guide for quantum chemical calculations of large molecules.

Buffer-gas cooling is a universal cooling technique for molecules and used for various purposes. One of its applications is using molecules inside a buffer-gas cell for low-temperature spectroscopy. Although a high-intensity signal is expected in the cell, complex molecular dynamics is a drawback for precise spectroscopy. In this study, we performed high-resolution absorption spectroscopy of low-J transitions in the Ã2 Π(0, 0, 0) − X2 Σ + (0, 0, 0) band of calcium monohydroxide (CaOH). CaOH molecules were produced by laser ablation in a copper cell and cooled to ∼5 K using helium buffer gas. We probed the Doppler effects in a buffer-gas cell by injecting counter-propagating lasers inside the cell. The time evolutions of the Doppler width and shift were simulated using a dedicated Monte Carlo simulation and compared with data.