The sixth chapter describes the bonding interaction in [PdAu24(C≡CArF)18−2n]2− (ArF = 3,5-(CF3)2C6H3) generated by the collision-induced dissociation (CID) of [PdAu24(C≡CArF)18]2− in the gas phase. The number of valence electrons of [PdAu24(C≡CArF)18−2n]2− was equal to 8 + 2n and did not agree with the discrete magic number of the spherical jellium model 8, 18, 20, and so on, suggesting the presence of the special binding mechanism of valence electrons. To elucidate the binding mechanism of excess valence electrons in CID products, anion photoelectron spectroscopy (PES) and density functional theory (DFT) calculation were conducted. Anion PES showed the gradual decrease of the electron binding energy with n. DFT calculation of the simplest fragment [PdAu24(C≡CArF)16]2− with 10 electrons showed that the removal of two ligands coordinating to the same Au atoms yielded the most plausible structure. The binding mechanism of the valence electrons in [PdAu24(C≡CArF)16]2− can be interpreted as the supervalence bonding of the PdAu12 core with 8 electrons and the Au2 unit with 2 electrons rather than a single superatom with 10 electrons. Therefore, [PdAu24(C≡CArF)16]2− was categorized to a heteronuclear superatomic molecule composed of superatoms with different electrons. The heteronuclear electron configuration persisted at the model structure of [PdAu24(C≡CArF)6]2− with 20 electrons.