Infrared reflection absorption spectroscopic study of the adsorption structures of dimethyl ether and methyl ethyl ether on Cu(111) and Ag(111)

Infrared reflection absorption (IRA) spectra measured for dimethyl ether (DME) adsorbed at 80 K on Cu(111) and Ag(111) give IR bands belonging only to the A(1) and B-2 species, indicating that the adsorbate takes on an orientation in which the C-2 axis bisecting the COC bond angle tilts away from the surface normal within the plane perpendicular to the substrates. The DFT method was applied to simulate the IRA spectra, indicating that the tilt angles of DME on Cu(111) and Ag(111) are about 50 degrees and 55 degrees, respectively, at sub-monolayer coverages. The results are in contrast to the case of DME on Cu(110) and Ag(110), where the C2 axis is perpendicular to the substrates [T. Kiyohara et al., J. Phys. Chem. A 106 (2002) 3469]. Methyl ethyl ether (MEE) adsorbed at 80 K on Cu(111) gives IRA bands mainly ascribable to the gauche (G) form, whereas the IRA spectra measured for MEE on Ag(111) are characterized by the trans (T) form. The rotational isomers are identical with those on Cu(110) and Ag(l 10); i.e., MEE on Cu(110) takes the G form and the adsorbate on Ag(110) the T form [T. Kiyohara et al., J. Phys. Chem. B 107 (2003) 5008]. The simulation of the IRA spectra indicated that (i) the G form adsorbate on Cu(111) takes an orientation, in which the axis bisecting the COC bond angle tilts away from the surface normal by ca. 30 degrees within the plane perpendicular to the surface to make the CH3-CH2 bond almost parallel to the surface, and (ii) the T form adsorbate on Ag(111) takes an orientation, in which the bisecting axis tilts away by ca. 60 degrees from the surface normal within the perpendicular plane. Comparison of these adsorption structures of MEE on the (111) substrates with those of MEE on Cu(110) and Ag(110) indicates that the structures are mainly determined by a coordination interaction of the oxygen atom to the surface metals and an attractive van der Waals interaction between the ethyl group of MEE and the substrate surfaces. The coordination interaction plays an important role on Cu(111) and Cu(110), which makes the adsorbate on the Cu substrates to take the orientations with the bisecting axis near parallel to the surface normal and to assume the G form in order to make the ethyl group parallel to the surface, which is favorable for the van der Waals interaction. In the case of MEE on the Ag substrates the attractive van der Waals interaction plays a dominant role, resulting in the T form which is more favorable for the interaction than the G form. (c) 2006 Elsevier B.V. All rights reserved.