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Electronegativity is a well-known property of atoms and substituent groups. Because there is no direct way to measure it, establishing a useful scale for electronegativity often entails correlating it to another chemical parameter; a wide variety of methods have been proposed over the past 80 years to do just that. This work reports a new approach that connects electronegativity to a spectroscopic parameter derived from resonant inelastic x-ray scattering. The new method is demonstrated using a series of chlorine-containing compounds, focusing on the Cl 2p−1LUMO1 electronic states reached after Cl 1s→LUMO core excitation and subsequent KL radiative decay. Based on an electron-density analysis of the LUMOs, the relative weights of the Cl 2pz atomic orbital contributing to the Cl 2p3/2 molecular spin-orbit components are shown to yield a linear electronegativity scale consistent with previous approaches.


Biological and Chemical Physics | Chemistry | Physics

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