To see C2: Single-photon ionization of the dicarbon molecule

• Published in: The Journal of chemical physics 2020-01, Vol.152 (4), p.041105-041105
• Main Authors: Harper, Oliver J., Boyé-Péronne, Séverine, Garcia, Gustavo A., Hrodmarsson, Helgi R., Loison, Jean-Christophe, Gans, Bérenger
• Format: Article
• Language: English
• Subjects: Adiabatic flow; Astronomical models; Cations; Computer simulation; Electric discharges; Electron states; Electron transitions; Enthalpy; Ground state; Imaging techniques; Ionization potentials; Photochemistry; Photons; Synchrotron radiation; Vapor phases
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.5139309

The C2 carbon cluster is found in a large variety of environments including flames, electric discharges, and astrophysical media. Due to spin-selection rules, assessing a complete overview of the dense vibronic landscape of the C2+ cation starting from the ground electronic state X Σg+1 of the neutral is not possible, especially since the C2+ ground state is of X+ Σg−4 symmetry. In this work, a flow-tube reactor source is employed to generate the neutral C2 in a mixture of both the lowest singlet X Σg+1 and triplet a 3Πu electronic states. We have investigated the vibronic transitions in the vicinity of the first adiabatic ionization potential via one-photon ionization with vacuum ultraviolet synchrotron radiation coupled with electron/ion double imaging techniques. Using ab initio calculations and Franck-Condon simulations, three electronic transitions are identified and their adiabatic ionization energy is determined Ei(a+ 2Πu←X 1Σg+)=12.440(10) eV, Ei(X+ 4Σg−←a 3Πu)=11.795(10) eV, and Ei(a+2Πu ← a3Πu) = 12.361(10) eV. From the three origin bands, the following energy differences are extracted: ΔE(a − X) = 0.079(10) eV and ΔE(a+ − X+) = 0.567(10) eV. The adiabatic ionization potential corresponding to the forbidden one-photon transition X+ ← X is derived and amounts to 11.873(10) eV, in very good agreement with the most recent measurement by Krechkivska et al. [J. Chem. Phys. 144, 144305 (2016)]. The enthalpy of formation of the doublet ground state C2+ cation in the gas phase is determined at 0 K, ΔfH0(0K)(C2+(Πu2))=2019.9(10) kJ mol−1. In addition, we report the first experimental ion yield of C2 for which only a simple estimate was used up to now in the photochemistry models of astrophysical media due to the lack of experimental data.