Ab initio-guided X-ray photoelectron spectroscopy quantification of Ti vacancies in <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" altimg="si24.svg"><mml:mrow><mml:msub><mml:mtext>Ti</mml:mtext><mml:mrow><mml:mn>1</mml:mn><mml:mo>?</mml:mo><mml:mi>?</mml:mi></mml:mrow></mml:msub><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mi>x</mml:mi></mml:msub><mml:msub><mml:mi mathvariant="normal">N</mml:mi><mml:mrow><mml:mn>1</mml:mn><mml:mo>?</mml:mo><mml:mi>x</mml:mi></mml:mrow></mml:…

Ab initio calculations were employed to investigate the effect of oxygen concentration dependent Ti vacancies formation on core electron binding energy shifts in cubic titanium oxynitride (Ti1??OxN1?x). It was shown, that presence a vacancy reduces 1s first N neighbors by ?0.6 eV and this is additive with respect number vacancies. Hence it predicted can be revealed from intensity shifted components spectra region. This notion critically appraised fitting region obtained via X-ray photoelectron spectroscopy (XPS) measurements Ti1??OxN1?x thin films deposited high power pulsed magnetron sputtering. A model quantify based ratio between signal components, corresponding atoms locally different concentration, developed. Herein random distribution assumed influence surface oxidation atmospheric exposure after deposition considered. The so estimated concentrations are consistent calculating O determined elastic recoil detection analysis text book states hence electroneutrality. Thus, we have unequivocally established population quantified XPS shifts.