Solving the CH_{4}^{-} Riddle: The Fundamental Role of Spin to Explain Metastable Anionic Methane.

Several types of experiments showed the existence of negative methane ions CH_{4}^{-} over a period of 50 years but the nature of this elusive species remains unknown. A benchmark study has shown that the experimentally observed species cannot be described by the attachment of an electron in the doublet ground state of CH_{4}^{-}. Here we find CH_{4}^{-} as being a metastable species in its lowest quartet spin state, a CH_{2}^{-}:H_{2} exciplex with three open shells lying ca. 10 eV above the methane singlet ground state but slightly below the dissociation fragments. The formation of charged high-spin exciplexes is a novel mechanism to explain small molecular anions with implications in a plethora of basic and applied research fields.