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Soft x-ray absorption (SXAS) and emission (SXES) spectroscopies were applied to study the nitrogen bonding structure in magnetron sputtered CNx thin films. By comparing with calculated spectra of N in different model systems, N in three main bonding environments can be identified: (i) C≡N bonds, with a sharp SXAS peak at 399.5 eV, (ii) pyridine-like N (i.e., N bonded to two C atoms), with an x-ray absorption resonance at ∼398.5 eV, and (iii) N substituted in graphite, possibly with one sp3 carbon as a neighbor (SXAS energy ∼401 eV). These bondings are present in all CNx films analyzed; however, as shown earlier, the relative intensities between the peaks may vary with the growth conditions. Differences in the coordination of the nearest or second nearest C neighbors only cause slight changes in the peak positions and spectrum shape.

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Although resonant x-ray scattering of molecules fulfills strict electronic symmetry selection rules, as now firmly proven by spectra of diatomic molecules, the accumulated body of data for polyatomic molecules indicates that an apparent breaking of these rules represents the common situation rather than the exception. The CO2 molecule provides a good example of symmetry breaking, with the oxygen x-ray emission spectra showing strong intensity for transitions that are forbidden by the parity selection rule. We present time-independent and time-dependent theories for frequency-dependent resonant x-ray scattering beyond the Born–Oppenheimer approximation in order to explore under what circumstances one can anticipate symmetry breaking in the spectra of polyatomic molecules. The theory starts out from the Kramers–Heisenberg dispersion relation and is generalized for vibrational degrees of freedom and for nonadiabatic coupling of the electronic (vibronic) states, including the frequency dependency of the scattering cross section. Different limiting cases and few-level models are considered. The symmetry breaking is proven to be the result of pseudo-Jahn–Teller-like vibronic coupling between near-degenerate core-excited states. Thus vibronic interaction over the antisymmetric vibrational mode between the “bright” 1σg−12πu1 and “dark” 1σu−12πu1 intermediate states of CO2 allows transitions otherwise forbidden. The measurements and theory demonstrate that the symmetry-selective character of the resonant x-ray emission is strongly frequency dependent. The strong intensity of “dipole-forbidden” transitions in the π* oxygen K spectrum at resonance is reduced monotonically with the detuning of the excitation energy from resonance, and the spectra become “symmetry purified.” Simulations with full vibronic coupling predict this feature of the x-ray scattering experiment and a few-level model explains the energy dependence of the symmetry selection and the symmetry purification at large detuning energies in the limit of narrowband photon excitation.

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