Probing a molecular electronic transition by two-colour sum-frequency generation spectroscopy

We demonstrate that a new emerging technique, two-colour sum-frequency generation (SFG) spectroscopy, can be used to probe the molecular electronic properties of self-assembled monolayers (SAMs). In the CH spectral range (2800–3200 cm-1), we show that the sum-frequency generation signal of a porphyrin alkanethiol derivative adsorbed on Pt(1 1 1) reaches a maximum intensity at ~435 nm SFG wavelength. This wavelength corresponds to the porphyrin moiety specific p–p*$ molecular electronic transition which is called the Soret or B band. This resonant behaviour is not observed for 1-dodecanethiol SAMs, which are devoid of molecular electronic transition in the investigated visible spectral range.