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While each atom species in PbSe corresponds to a single crystallographic site and transport measurements reveal a single carrier density, super(207)Pb NMR reveals a more complicated picture than previously thought comprising three discrete homogeneous carrier components, each associated with n- or p-type carrier fractions. The origins of these fractions are discussed in terms of electronic heterogeneity of the native semiconductor. The interaction mechanism between nuclear spins and lattice vibrations via fluctuating spin-rotation interaction, applicable to heavy spin-1/2 nuclei [Phys. Rev. B 74, 214420 (2006) (http://dx.doi.org/10.1103/PhysRevB.74.214420)], does not hold. Instead, a higher-order temperature dependence dominates the relaxation pathway. Shallow acceptor states and deep level defects in the midgap explain the complex temperature dependence of the direct band gap.