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The feasibility of satisfying the Ridley–Watkins–Hilsum conditions for negative differential resistance (NDR) effect in the ternary Nowotny-Juza semiconductors LiZnAs and LiCdAs is explored through first-principles computations. Both compounds, which adopt the half-Heusler crystal structure, are characterized via density-functional band structure calculation and effective mass evaluation. This work provides a detailed account of conduction band energies and effective masses in the , X, and L valleys, while also probing the effect of external pressure on such critical properties and the ensuing potential for NDR. When compared to their binary analogs, GaAs and InAs, the above filled tetrahedral semiconductors are shown to potentially hold an advantage governed by the ’tetrahedral interstitial insertion rule.’ This finding underscores their promise for experimental studies aimed at harnessing the Gunn effect and NDR for high-frequency microwave oscillations and electromagnetic wave emission.