Protocol for optically pumping AlH⁺to a pure quantum state

We propose an optical pumping scheme to prepare trapped AlH+ molecules in a pure state, the stretched hyperfine state (Formula Presented) of the rovibronic ground manifold |X2Σ+, v = 0, N = 0 〉. Our scheme utilizes linearly-polarized and circularly-polarized fields of a broadband pulsed laser to cool the rotational degree of freedom and drive the population to the hyperfine state, respectively. We simulate the population dynamics by solving a representative system of rate equations that accounts for the laser fields, blackbody radiation, and spontaneous emission. In order to model the hyperfine structure, new hyperfine constants of the A2Π excited state were computed using a RASSCF wavefunction. We find that adding an infrared laser to drive the 1-0 vibrational transition within the X2Σ+ manifold accelerates the cooling process. The results show that, under optimal conditions, the population in the target state of the rovibronic ground manifold can reach 63% after 68 μs (330 ms) and 95% after 25 ms (1.2 s) with (without) the infrared laser.