ABSTRACT
High-resolution velocity-map imaged photoelectron spectra of the ethynyl anions C2H- and C2D- are measured at photon wavelengths between 355 and 266 nm to investigate the complex interactions between the closely lying XÌ2Σ+ and Ã2Π electronic states. An indicative kinetic energy resolution of 0.4%, together with the full angular dependence of the fast electrons, provides a detailed description of the vibronically coupled structure. It is demonstrated that a modest quadratic vibronic coupling model, parameterized by the quasidiabatic ansatz, is sufficient to accurately recreate all the observed vibronic interactions. Simulated spectra are shown to be in excellent agreement with the experimental data, verifying the proposed model and providing a framework that may be used to accurately simulate spectra of larger C2nH monohydride carbon chains. New spectral assignments are supported by experimental electron anisotropy measurements and Dyson orbital calculations.
ABSTRACT
Polycyclic aromatic hydrocarbons (PAHs) are intermediates in the formation of soot particles and interstellar grains. However, their formation mechanisms in combustion and interstellar environments are not fully understood. The production of tricyclic PAHs and, in particular, the conversion of a PAH containing a five-membered ring to one with a six-membered ring are of interest to explain PAH abundances in combustion processes. In the present work, resonant ionization mass spectrometry in conjunction with isotopic labeling is used to investigate the formation of the phenalenyl radical from acenaphthylene and methane in an electrical discharge. We show that in this environment the CH cycloaddition mechanism converts a five-membered ring to a six-membered ring. This mechanism can occur in tandem with other PAH formation mechanisms such as hydrogen abstraction/acetylene addition (HACA) to produce larger PAHs in flames and the interstellar medium.
ABSTRACT
Weakly bound anionic systems present a new domain for negative ion spectroscopy. Here we report on a multifaceted study of the CH2CN- dipole-bound state, employing high-resolution photoelectron spectroscopy from 130 different wavelengths, velocity-map imaging at threshold, and laser scanning photodetachment experiments. This uncovers a wide variety of different vibrational and rotational autodetaching resonances. By examination of both sides of the problem, absorption from the anion to the dipole-bound state and vibrational/rotational autodetachment to the neutral, a complete model of the dipole-bound chemistry is formed. Precise values for the electron affinity EA = 12468.9(1) cm-1, dipole binding energy DBE = 40.2(3) cm-1, and anion inversion splitting ω5 = 115.9(2) cm-1 are obtained. This model is then employed to study possible astronomical implications, revealing good agreement between the K = 1 â 0 CH2CN- dipole transition and the λ8040 diffuse interstellar band.
