Adsorption of benzonitrile onSi(001)−2×1at 300 K

Probing charge transfer dynamics in self-assembled monolayers by core hole clock approach

“…As a result, the degeneracy of the former orbital is lifted and it splits into two states with different energies, polarized either perpendicular ( 1 *) or parallel ( 3 *) to the ring plane (see Fig. 10), in good agreement with the previous theoretical and experimental work [77,78]. The lower intensity of the 1 * resonance as compared to the 3 * one is related to the delocalization of the 1 * orbital over the entire benzonitrile moiety, whereas 3 * is localized on the nitrile group.…”

“…The spectra are dominated by a double, *-like resonance at ∼398.8 and ∼399.75 eV, with these PE positions being almost identical for all benzonitrile-terminated SAMs studied. This spectrum resembles that of benzonitrile [77,78] and is typical of SAMs containing this group [56,58,79]. The appearance of the double resonance instead of the single one as for NC-Cn/Au (Fig.…”

Reaction of acetonitrile with the silicon(001) surface: A combined XPS and FTIR study

“…The singlebonded molecule shown in Fig. 7a requires cleavage of one C-H bond and was previously considered (but rejected) as a potential adsorption product [21]. The products shown in Fig.…”

“…Previous studies of acetonitrile interacting with Si(0 0 1) have identified the four-member ring shown in Fig. 5a as one product of acetonitrile adsorption [15,18,21]. While this structure is formally identical to the product of a [2 + 2] cycloaddition reaction of the Si@Si dimer with the C"N bond, theoretical studies have reported that it likely forms through a dative-bonded intermediate [23,36], in agreement with studies of analogous reactions in the organic chemistry literature [37].…”

“…Several studies indicate that nitriles react with Si(0 0 1) [13][14][15][16][17][18][19][20][21][22], yet mechanistic details for the simplest nitrile systems remain unclear due to the complication of several products being formed [13][14][15][16][19][20][21]23]. In particular, it has been shown that acetonitrile forms several products at room temperature although this is the functionally simplest nitrile system in terms of available reactive groups [15,[19][20][21]23]. In this paper, we have investigated the chemistry of acetonitrile on the Si(0 0 1) surface to gain a more complete understanding of the products that are formed and to better sort out mechanistic details of this complicated reaction.…”