Experimental and theoretical threshold photoelectron spectra of methylene

• Published in: The Journal of chemical physics 2018-12, Vol.149 (22), p.224304-224304
• Main Authors: Coudert, L. H., Gans, B., Holzmeier, F., Loison, J.-C., Garcia, G. A., Alcaraz, C., Lopes, A., Röder, A.
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Ionization potentials; Methylene; Nonlinearity; or physical chemistry; Photoelectrons; Physics; Synchrotron radiation; Theoretical and; Water chemistry
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.5062834

The threshold photoelectron spectrum of methylene (CH2), produced by consecutive H atom abstractions on methane, has been recorded using synchrotron radiation. The experimental spectrum spans the region of the X+ 2Πu ← X 3B1 ionizing transition. It is modeled starting from ab initio bending potentials and using the bending approach introduced by Coudert et al. [J. Chem. Phys. 148, 054302 (2018)] accounting for the quasilinearity of CH2 and the strong Renner-Teller interaction in CH2+. This first calculation yields a theoretical threshold photoelectron spectrum which is in moderate agreement with the experimental one. A more accurate approach treating the three vibrational modes is developed for computing the threshold photoelectron spectrum of triatomic C2v molecules. This new treatment is tested modeling the already measured threshold photoelectron spectrum of the X+ 2Πu ← X 1A1 ionizing transition of the water molecule. The threshold photoelectron spectrum of CH2 computed with the new approach compares more favorably with the experimental spectrum and yields an adiabatic ionization potential of 10.386(6) eV.