A Correction Scheme for Fano Line Shapes in Two-Dimensional Infrared Spectroscopy

Abstract

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 sputter-coated metal layer (Au). The correction scheme reveals conventional, easily interpretable 2D IR spectra.