A new method to derive electronegativity from resonant inelastic x-ray scattering

Area of Science:

• Quantum Chemistry
• Spectroscopy
• Chemical Physics

Background:

• Electronegativity is a fundamental atomic property crucial for understanding chemical bonding.
• Existing methods for quantifying electronegativity rely on indirect correlations with other chemical parameters.
• A direct and reliable measurement of electronegativity remains a challenge in chemistry.

Purpose of the Study:

• To develop a new, direct method for establishing an electronegativity scale.
• To correlate electronegativity with spectroscopic data obtained from resonant inelastic X-ray scattering (RIXS).
• To validate the new method using a series of chlorine-containing compounds.

Main Methods:

• Utilized resonant inelastic X-ray scattering (RIXS) to probe electronic states.
• Focused on Cl 2p(-1)LUMO(1) electronic states following Cl 1s → LUMO core excitation and KL radiative decay.
• Performed electron-density analysis of the lowest unoccupied molecular orbitals (LUMOs).

Main Results:

• Established a linear electronegativity scale based on RIXS data.
• Demonstrated the method's consistency with established electronegativity scales.
• Quantified the contribution of the Cl 2p(z) atomic orbital to molecular spin-orbit components.

Conclusions:

• Resonant inelastic X-ray scattering offers a novel spectroscopic route to determine atomic electronegativity.
• The proposed method provides a reliable and consistent linear scale for electronegativity.
• This work advances the understanding and measurement of a key chemical property.