The effect of substitution on the potential energy surfaces of triple-bonded RGa PR (R = F, OH, H, CH3, SiH3, SiMe(SitBu(3))(2), SiiPrDis(2), Tbt (C6H2-2,4,6-{CH(SiMe3)(2)}(3)), and Ar* (C6H3-2,6-(C6H2-2,4,6-i-Pr-3)(2))) compounds was theoretically examined by using density functional theory (i.e., M06-2X/Def2-TZVP, B3PW91/Def2-TZVP, and B3LYP/LANL2DZ+dp). The theoretical evidence strongly suggests that all of the triple-bonded RGa PR species prefer to select a bent form with an angle (