Effects of Symmetry on Intense-field Ionization of Heterocyclic Organic Molecules

We report on the ultrafast photoionization of pyridine, pyridazine, pyrimidine and pyrazine. These four molecules represent a systematic series of perturbations into the structure of a benzene ring which explores the substitution of a C-H entity with a nitrogen atom, creating a heterocyclic structure which remains isoelectronic with benzene. Other than pyridine, each molecule has the same molecular formula, with the only difference being the placement of the perturbing nitrogen atoms (ortho-, meta- or para-substitutions). Differences in the intense-field behavior of these molecules are caused by the symmetry of the perturbation to the benzene system, primarily influenced through the interactions of lone-pair states surrounding the nitrogen atoms. Data is recorded under intense-field, single-molecule conditions. 50 fs, 800 nm pulses are focused into the molecular vapor, and ion mass spectra are recorded for intensities of $\sim $10$^{13}$ W/cm$^{2}$ to $\sim $10$^{15}$ W/cm$^{2}$. We measure ion yields in the absence of the focal volume effect without the need for deconvolution of the data. For all targets, stable singly- and doubly-charged parent ions (C$_{6-n}$H$_{6-n}$N$_{n}^{+(+)})$ are observed with features suggesting resonance enhancement (REMPI).