A Correction Scheme for Fano Lineshapes in Two-Dimensional Infrared Spectroscopy.

The asymmetry of Fano line shapes observed for metal-adsorbate systems is reflected in two-dimensional infrared (2D IR) spectroscopy as a distorted spectrum. A phenomenological correction scheme is proposed that transforms distorted 2D IR spectra into conventional spectra. To that end, a phase correction factor is first derived from the IR absorption spectrum of the sample by symmetrizing the asymmetric line shape and subsequently applied to the distorted 2D IR spectra. The concept is illustrated for a model system consisting of an organic molecule (p-mercaptobenzonitrile) adsorbed on a sputtercoated metal layer (Au). The correction scheme reveals conventional, easily interpretable 2D IR spectra.