title: Temperature effects in the vibrational spectra of self-assembled monolayers.
abstract: The vibrational spectrum of a thiolate-based self-assembled monolayer fabricated by the adsorption of benzylmercaptan on a Au(111) substrate is studied using a combined experimental and theoretical approach employing infrared reflection absorption spectroscopy and density functional theory. The vibrational spectra are derived both using a finite differences approach and from ab initio molecular dynamics simulations at various temperatures. In addition, the possibility of adsorbate-induced reconstructions of the Au(111) substrate is taken into account. It turns out that the measured spectra can only be understood by taking finite temperatures into account.
authors.affiliation: Helmholtz Institute Ulm (HIU) Electrochemical Energy Storage, D-89069 Ulm, Germany and Institute of Theoretical Chemistry, Ulm University, D-89069 Ulm, Germany.
authors.forename: Katrin
authors.initials: K
authors.lastname: Forster-Tonigold
authors.forename: Xia
authors.initials: X
authors.lastname: Stammer
authors.forename: Christof
authors.initials: C
authors.lastname: Wöll
authors.forename: Axel
authors.initials: A
authors.lastname: Groß