Since its successful preparation in 2004, graphene has attracted a great deal of attention, and the sensing application is an important research field. But nearly all the researches about graphene sensors focus on low frequency band, of which the mechanism is mainly dependent on the detection of charge carrier concentration and conductivity variation induced by the absorption of molecules. However, due to the fact that most of the molecules absorbed on the surface of graphene will induce the change of conductivity, this method is incapable of distinguishing different molecules. Transmission mode of a single molecular layer is studied based on Kubo formula and combined with a numerical method. The relation between transmission properties and effective mode index is analyzed, and the broadband localization capability of the waveguide mode is demonstrated. Meanwhile, the variation of the transmission intensity which is due to the interaction between the first order waveguide mode and the gas is adopted to retrieve the vibration spectrum of molecules. Taking the sensing of SO2, CO and C7H8 as examples, the effectiveness of this method is verified based on eigenmode analysis. Results show that the transmission spectrum is consistent with the variation spectrum of gas molecules; besides, in the transmission direction, the larger the interaction range, the greater the attenuation of mode transmission intensity will be. This study has provided a theoretical foundation for the realization of the detection and identification of gas moleculan fingerprints.