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              <p>The negatively-charged boron vacancy (V - B ) center in hexagonal boron nitride (hBN) is currently garnering considerable attention for the design of two-dimensional (2D) quantum sensing units. Such developments require a precise understanding of the spin-dependent optical response of V - B centers, which still remains poorly documented despite its key role for sensing applications. Here we investigate the spin-dependent photodynamics of V - B centers in hBN by a series of time-resolved photoluminescence (PL) measurements. We first introduce a robust all-optical method to infer the spin-dependent lifetime of the excited states and the electron spin polarization of V - B centers under optical pumping. Using these results, we then analyze PL time traces recorded at different optical excitation powers with a seven-level model of the V - B center and we extract all the rates involved in the spin-dependent optical cycles, both under ambient conditions and at liquid helium temperature. These findings are finally used to study the impact of a vector magnetic field on the optical response. More precisely, we analyze PL quenching effects resulting from electron spin mixing induced by the magnetic field component perpendicular to the V - B quantization axis. All experimental results are well reproduced by the seven-level model, illustrating its robustness to describe the spin-dependent photodymanics of V - B centers. This work provides important insights into the properties of V - B centers in hBN, which are valuable for future developments of 2D quantum sensing units.</p>
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