The molecular orbital energies at the L-point are drawn in Figure , in accordance with the DFT results. Since the atomic orbital energies of the cation are higher than those of the anion, the conduction and valence band edges are primarily com- posed of cation-p and anion-p orbitals, respectively (Figure ). The molecular orbitals of the rock-salt IV-VI compounds arise from nearest-neighbor s/p-interactions between the cation and anion, as well as further splitting of the p-orbital energies by nextnearest-neighbor p/p-interactions. Cation-p and anion-p orbitals do not interact at the L-point due to symmetry restrictions. The band edge states have distinct symmetries, which we label L - 6 and L + 6 following the naming convention of Ref. 31. The conduction and valence band edge states have L - 6 and L + 6 symmetry, respectively, when the bands are not inverted, whereas the symmetries are flipped when the bands are inverted (Figure ). It is clear from the diagram that one route to tune the band inversion parameter M 0 is by modulating the nearest-neighbor s/p interaction. The conduction band edge state in a compound with normal band ordering results from the hybridization between cation-p and anion-s orbitals (Figure ), so decreasing the cation-p/anion-s interaction V Sn p -Se s would lower the energy of the L - 6 state. Similarly, the L + 6 valence band edge state results from the interaction between the anion-p and cation-s orbitals, so increasing the cation-s/anion-p interaction V Sn s -Se p would raise the energy of the L + 6 state. This can also be seen from Equation (4). Tuning the interaction energies in such a way will result in the inversion of the L - 6 and L + 6 states (Figure ). Tuning the chemical interaction strengths to achieve high valley degeneracy can be done in several ways, for example by alloying and mechanical deformation. To induce multiple carrier pockets in SnTe, we suggest alloying the compound with either SnSe or SnS. While SnSe and SnS natively crystallize in the layered orthorhombic Pnma structure, single-phase alloys between SnTe and SnSe in the rock-salt structure have been reported, indicating that the rock-salt crystal structure can be maintained up to a solubility limit. Given that the s-and p-orbital energies of Se and S are lower than those of Te, we would expect the Sns/anion-p interaction to strengthen since the atomic orbital energies will be closer, resulting in an increase in the energy of the L + 6 state. Similarly, we would expect the Sn-p/anion-s interaction to weaken since the energy separation between the Sn-p and the anion-s atomic orbitals will be larger, resulting in a decrease in the energy of the L - 6 state. While it is certainly not guaranteed that simply increasing/decreasing the chemical interactions will lead to multiple carrier pockets, we emphasize that exaggerating the interaction strengths to invert the bands enough is the key criteria for engineering high valley degeneracy. We suggest revisiting such alloys in light of the present study, as our model predicts a 6× increase in the valley degeneracy of SnTe to N V = 24.