Recently it was pointed out that transition frequencies in certain diatomic molecules have an enhanced sensitivity to variations in the fine-structure constant and the proton-to-electron mass ratio due to a near cancellation between the fine-structure and vibrational interval in a ground electronic multiplet [V.~V.~Flambaum and M.~G.~Kozlov, Phys. Rev. Lett.~{\bf 99}, 150801 (2007)]. One such molecule possessing this favorable quality is silicon monobromide. Here we take a closer examination of SiBr as a candidate for detecting variations in and . We analyze the rovibronic spectrum by employing the most accurate experimental data available in the literature and perform \emph{ab initio} calculations to determine the precise dependence of the spectrum on variations in . Furthermore, we calculate the natural linewidths of the rovibronic levels, which place a fundamental limit on the accuracy to which variations may be determined.

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