Thermochemical electronegativities of the elements

Electronegativity is a key property of the elements. Being useful in rationalizing stability, structure and properties of molecules and solids, it has shaped much of the thinking in the fields of structural chemistry and solid state chemistry and physics. There are many definitions of electronegativity, which can be roughly classified as either spectroscopic (these are defined for isolated atoms) or thermochemical (characterizing bond energies and heats of formation of compounds). The most widely used is the thermochemical Pauling's scale, where electronegativities have units of eV(-1/2). Here we identify drawbacks in the definition of Pauling's electronegativity scale-and, correcting them, arrive at our thermochemical scale, where electronegativities are dimensionless numbers. Our scale displays intuitively correct trends for the 118 elements and leads to an improved description of chemical bonding (e.g., bond polarity) and thermochemistry. Pauling's electronegativity scale has a fundamental value and uses accessible thermochemical data, but fails at predicting the bonding behavior for several elements. The authors propose their thermochemical scale based on experimental dissociation energies that provides dimensionless values for the electronegativity and recovers the correct trends throughout the periodic table.

Automated summary

Electronegativity is a key property of the elements that plays an important role in structural chemistry and solid state chemistry and physics. The widely used thermochemical Pauling scale has drawbacks, leading the authors to propose a new thermochemical scale based on experimental dissociation energies that provides dimensionless values for electronegativity. This new scale corrects the flaws in the Pauling scale and improves the description of chemical bonding and thermochemistry.