Electron-induced proton transfer depicts the proton motion coupled with the attachment of a low-energy electron to a molecule, which helps to understand copious fundamental chemical processes. Intramolecular electron-induced proton transfer is a similar process that occurs within a single molecule. To date, there is only one known intramolecular example, to the best of our knowledge. By studying the 10-hydroxybenzo[h]quinoline and 8-hydroxyquinoline molecules using anion photoelectron spectroscopy and density functional theory, and by theoretical screening of six other molecules, here we show the intramolecular electron-induced proton transfer capability of a long list of molecules that meanwhile have the excited-state intramolecular proton transfer property. Careful examination of the intrinsic electronic signatures of these molecules reveals that these two distinct processes should occur to the same category of molecules. Intramolecular electron-induced proton transfer could have potential applications such as molecular devices that are responsive to electrons or current.

The low energy photoionization spectrum of propyne (CH3-CCH), which reveals the vibronic structure of the propyne cation, is simulated using vibronic coupling theory. The spin-orbit interaction is included using an intensity borrowing approach, enabling determination of the (X̃(2)E1/2,3/2, v = 0) splitting and the relative photoionization intensity of these closely spaced levels. The results are compared with recent experimental studies and misstatements are corrected.

Elucidating the multifaceted processes of molecular activation and subsequent reactions gives a fundamental view into the development of iridium catalysts as they apply to fuels and propellants, for example, for spacecraft thrusters. Hydroxylamine, a component of the well-known hydroxyl­ammonium nitrate (HAN) ionic liquid, is a safer alternative and mimics the chemistry and performance standards of hydrazine. The activation of hydroxylamine by anionic iridium clusters, Ir n – (n = 1–5), depicts a part of the mechanism, where two hydrogen atoms are removed, likely as H2, and Ir n (NOH)− clusters remain. The significant photoelectron spectral differences between these products and the bare clusters illustrate the substantial electronic changes imposed by the hydroxylamine fragment on the iridium clusters. In combination with DFT calculations, a preliminary reaction mechanism is proposed, identifying the possible intermediate steps leading to the formation of Ir­(NOH)−.