Single molecule infrared spectroscopy in the gas phase

Spectroscopy is a key analytical tool that provides valuable insight into molecular structure and is widely used to identify chemical samples. Tagging spectroscopy is a form of action spectroscopy in which the absorption of a single photon by a molecular ion is detected via the loss of a weakly attached, inert ‘tag’ particle (for example, He, Ne, N 2 ) 1 – 3 . The absorption spectrum is derived from the tag loss rate as a function of incident radiation frequency. So far, all spectroscopy of gas phase polyatomic molecules has been restricted to large molecular ensembles, thus complicating spectral interpretation by the presence of multiple chemical and isomeric species. Here we present a novel tagging spectroscopic scheme to analyse the purest possible sample: a single gas phase molecule. We demonstrate this technique with the measurement of the infrared spectrum of a single gas phase tropylium (C 7 H 7 + ) molecular ion. The high sensitivity of our method revealed spectral features not previously observed using traditional tagging methods 4 . Our approach, in principle, enables analysis of multicomponent mixtures by identifying constituent molecules one at a time. Single molecule sensitivity extends action spectroscopy to rare samples, such as those of extraterrestrial origin 5 , 6 , or to reactive reaction intermediates formed at number densities that are too low for traditional action methods. Using tagging spectroscopy, the infrared spectrum of a single organic molecule in the gas phase has been successfully measured.