Electron transfer capability in atomic hydrogen reactions for imidazole groups bound to the insulating alkanethiolate layer on Au(111)

Kato, Hiroyuki S.*; Muroyama, Mizuho*; Kobayakawa, Nano*; Muneyasu, Riku*; Tsuda, Yasutaka   ; Murase, Natsumi*; Watanabe, Seiya*; Yamada, Takashi*; Kanematsu, Yusuke*; Tachikawa, Masanori*; Akai-Kasaya, Megumi*; Okada, Michio*; Yoshigoe, Akitaka 

The charge transfer capability associated with chemical reactions at metal-organic interfaces was studied via the atomic H addition reaction for an imidazole-terminated alkanethiolate self-assembled monolayer (Im-SAM) film on Au(111) using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, infrared reflection absorption spectroscopy (IRAS), work function measurements, and density functional theory (DFT) calculations. The imidazolium cation is a stable species in liquids, therefore, it is pertinent to determine whether the hydrogenation reactions of the imidazole groups produce imidazolium cations accompanied by electron transfer to the Au substrate, even in the absence of solvate and/or counterions on the insulating alkanethiolate layer. The analyses indicated that the imidazolium moieties in Im-SAM formed during atomic H irradiation, and some of the imidazolium radicals became cations. Theoretical model calculations also revealed that the total energies and molecular orbital levels satisfied the imidazolium cation formation associated with electron transfer.