7
$\begingroup$

As the title asks, is it possible to calculate the electronegativity (EN) of specific atoms on extended surfaces (slabs), more specifically using computational methods? There are a few issues here I am running into:

To find the Mulliken EN $\chi$, we can use the relation

$$\chi = \frac{E_\mathrm{i} + E_\mathrm{ea}}{2}$$

where $E_\mathrm{i} = E(\ce{M+}) - E(\ce{M})$ and $E_\mathrm{ea} = E(\ce{M})-E(\ce{M-})$. However, these energies are for the entire system, usually a molecule, and not the individual atoms. I hope I am not misunderstanding the concept here.

Alternatively certain definitions use $\chi = -\mu$, or the work function. Again, this is usually calculated on a surface basis, not per atom of site.

Is there no accurate determination method which is specific to the atom? Or is it conceptually impossible?

$\endgroup$

Your Answer

By clicking “Post Your Answer”, you agree to our terms of service, privacy policy and cookie policy