title: Ab initio modeling of defect signatures in infrared reflection-absorption spectra of SAMs exposing methyl- and hydrogen-terminated oligo(ethylene glycols).
abstract: Extensive ab initio modeling has been performed to explain quantitatively the apparent shapes of characteristic bands, which are systematically observed in the fingerprint region of infrared (IR) reflection-absorption (RA) spectra of oligo(ethylene glycol) (OEG)-terminated SAMs. The presence of defects was thoroughly examined by modeling the RA spectra using the DFT method BP86/6-31G* for all-helical and all-trans conformers of HS(CH2CH2O)nR (n = 5, 6, R = H, CH3) and HS(CH2)15CONH(CH2CH2O)6H molecules and for several defect-containing conformers. These data were then used to simulate RA spectra of SAMs with different content of defects and to compare them with experiments. It is shown that for SAMs of HS(CH2CH2O)nCH3 (n = 5, 6) the pronounced asymmetry of the dominating band can be attributed to the multimode nature of COC stretching vibrations of helical conformers combined with the contribution from few percent of all-trans conformers. Arguments are presented which disprove appreciable amounts of helical conformers with single trans and/or gauche defects. Much more complex combination of factors, which can come into play in the formation of the high-frequency shoulder of COC band, is exemplified by self-assemblies of OEG-terminated amide-bridged alkanethiolates. In particular, spectral signatures of defects with inverted OH terminus are compared with other contributions to the apparent shape of COC band formation. For this family of SAMs, the presence of about 10% of all-trans conformers gives a satisfactory quantitative agreement between the calculated RA spectra and experimental observations.
authors.affiliation: Bogolyubov Institute for Theoretical Physics, 03680 Kyiv, Ukraine.
authors.forename: Lyuba
authors.initials: L
authors.lastname: Malysheva
authors.forename: Alexander
authors.initials: A
authors.lastname: Onipko
authors.forename: Bo
authors.initials: B
authors.lastname: Liedberg
mesh_terms: D006859:Hydrogen / Q000737:chemistry*; D008697:Methane / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D011092:Polyethylene Glycols / Q000737:chemistry*; D011789:Quantum Theory; D013055:Spectrophotometry, Infrared / Q000379:methods
chemical_list: D011092:Polyethylene Glycols; D006859:Hydrogen; D008697:Methane