The C 1s and N 1s near edge x-ray absorption fine structure spectra of five azabenzenes in the gas phase

• Published in: The Journal of chemical physics 2008-01, Vol.128 (4), p.044316-044316
• Main Authors: Vall-llosera, G, Gao, B, Kivimäki, A, Coreno, M, Alvarez Ruiz, J, de Simone, M, Agren, H, Rachlew, E
• Format: Article
• Language: English
• Subjects: ABSORPTION; ABSORPTION SPECTROSCOPY; Aza Compounds - chemistry; Benzene Derivatives - chemistry; Carbon - chemistry; DENSITY FUNCTIONAL METHOD; ELECTRONEGATIVITY; Electrons; Energy Transfer; FINE STRUCTURE; Gases; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; IONIZATION POTENTIAL; MOLECULAR ORBITAL METHOD; NATURAL SCIENCES; NATURVETENSKAP; Nitrogen - chemistry; Photons; PYRAZINES; Pyrazines - chemistry; PYRIDAZINES; PYRIDINE; Pyridines - chemistry; PYRIMIDINES; Pyrimidines - chemistry; RESONANCE; RYDBERG STATES; SPECTRA; Spectrum Analysis - methods; TRIAZINES; Triazines - chemistry; X RADIATION; X-RAY SPECTROSCOPY; X-Rays
• ISSN: 0021-9606; 1089-7690; 1089-7690
• DOI: 10.1063/1.2822985

Near edge x-ray absorption fine structure spectra have been measured and interpreted by means of density functional theory for five different azabenzenes (pyridine, pyridazine, pyrimidine, pyrazine, and s-triazine) in the gas phase. The experimental and theoretical spectra at the N 1s and C 1s edges show a strong resonance assigned to the transition of the 1s electron in the respective N or C atoms to the lowest unoccupied molecular orbital with pi(*) symmetry. As opposed to the N 1s edge, at the C 1s edge this resonance is split due to the different environments of the core hole atom in the molecule. The shift in atomic core-level energy due to a specific chemical environment is explained with the higher electronegativity of the N atom compared to the C atom. The remaining resonances below the ionization potential (IP) are assigned to sigma or pi [corrected] orbitals with mixed valence/Rydberg [corrected] character. Upon N addition, a reduction of intensity is observed in the Rydberg region at both edges as compared to the intensity in the continuum. Above the IP one or more resonances are seen and ascribed here to transitions to sigma(*) orbitals. Calculating the experimental and theoretical Delta(pi) term values at both edges, we observe that they are almost the same within +/-1 eV as expected for isoelectronic bonded pairs. The term values of the pi(*) and sigma(*) resonances are discussed in terms of the total Z number of the atoms participating in the bond.