Adsorption of acetonitrile (CH3 CN) on Si(111)-7x7 at room temperature studied by synchrotron radiation core-level spectroscopies and excited-state density functional theory calculations

The room temperature adsorption of acetonitrile (CH3 -C N) on Si(111)-7x7 is examined by synchrotron radiation N 1s x-ray photoemission and x-ray absorption spectroscopies. The experimental spectroscopic data point to multiple adsorption geometries. Candidate structures are optimized using density functional theory (DFT), the surface being simulated by silicon clusters encompassing one (adjacent) adatom-rest atom pair. This is followed by the DFT calculation of electron transition energies and cross sections. The comparison of theoretical spectra with experimental ones indicates that the molecule is adsorbed on the surface under two forms, a nondissociated geometry (an s p2 -hybridized CN) and a dissociated one (leading to a pendent sp-hybridized CN). In the nondissociative mode, the molecule bridges an adatom-rest atom pair. For bridge-type models, the discussion of the core-excited state calculations is focussed on the so-called silicon-molecule mixed-state transitions that strongly depend on the breaking or not of the adatom backbonds and on the attachment of the nitrogen end either to the adatom or to the rest atom. Concerning the dissociated state, the CH bond cleavage leads to a cyanomethyl (Si- CH2 -CN) plus a silicon monohydride, which accounts for the spectroscopic evidence of a free C N group (we do not find at 300 K any spectroscopic evidence for a C N group datively bonded to a silicon atom via its nitrogen lone pair). Therefore the reaction products of acetonitrile on Si(111)-7x7 are similar to those detected on the Si(001)-2x1 surface at the same temperature, despite the marked differences in the reconstruction of those two surfaces, especially the distance between adjacent silicon broken bonds. In that respect, we discuss how adatom backbond breaking in the course of adsorption may explain why both surface orientations react the same way with acetonitrile.