Temperature effects in the vibrational spectra of self-assembled monolayers
Katrin Forster-Tonigold1, Xia Stammer, Christof Wöll
1Helmholtz Institute Ulm (HIU) Electrochemical Energy Storage, D-89069 Ulm, Germany and Institute of Theoretical Chemistry, Ulm University, D-89069 Ulm, Germany.
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.
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