In simple terms, the collision of two atoms $\ce{A}$ and $\ce{B}$ will result in ions $\ce{A^+}$ and $\ce{B^-}$ if $$I_a(\ce{A})+E_a(\ce{A})<I_a(\ce{B})+E_a(\ce{B})$$ where $I_a$ and $E_a$ are the ionisation energies and electron affinities, respectively. Let us view $\ce{A^+B^-}$ as a molecule of sorts, having ions of rigid, non-polarisable spheres. Say $r$ is the sum of the radii of such spheres. The potential energy $E_p$ of such a system would then be $$E_p=I_a(\ce{A})-E_a(\ce{B})-\frac{e^2}{r}+\frac{b}{r^n}.$$

It is intuitive that

• the term $I_a(\ce{A})-E_a(\ce{B})$ characterises the energy required to form isolated ions $\ce{A^+}$ and $\ce{B^-}$ in the gas phase;
• $-e^2/r$ takes into account culonic attraction between two ions.

It is not intuitive for me why the final term is how it is.

The final term, introduced by Max Born, encompasses the repulsion generated by shells of electrons at either ion.

Of course, such effects cannot be ignored. But I am interested in why is it $b/r^n$. What is the justification? Feel free to provide the rigorous approach, even though it will probably$^{[1]}$ be above my abilities of comprehension.

Browsing on Wikipedia, the information might be given in the book Advanced Inorganic Chemistry by F. Albert Cotton, Geoffrey Wilkinson, Carlos A. Murillo, and Manfred Bochmann.

The pertinent section “1-6. Energetics of Ionic Crystals” starts at page 18$^{[2]}$, however I cannot find the derivation. There is only that the value of $n$ relies on a compressibility measurement, given as fractional change in volume per unit change in pressure, or

$$\frac{\Delta V}{V\Delta P}.$$

Also, this is seems somewhat contradictory to the earlier assumption of rigid spheres as written in another book$^{[3]}$. So, if anything, the linked book confused me further.

$^{[1]}$ Most certainly.

$^{[2]}$ Page 28 in the PDF.

$^{[3]}$ U. Palm, V. Past. Physical Chemistry. (1974) [To my knowledge, not available in English.]

In simple terms, the collision of two atoms $\ce{A}$ and $\ce{B}$ will result in ions $\ce{A^+}$ and $\ce{B^-}$ if $$I_a(\ce{A})+E_a(\ce{A})<I_a(\ce{B})+E_a(\ce{B})$$ where $I_a$ and $E_a$ are the ionisation energies and electron affinities, respectively. Let us view $\ce{A^+B^-}$ as a molecule of sorts, having ions of rigid, non-polarisable spheres. Say $r$ is the sum of the radii of such spheres. The potential energy $E_p$ of such a system would then be $$E_p=I_a(\ce{A})-E_a(\ce{B})-\frac{e^2}{r}+\frac{b}{r^n}.$$

It is intuitive that

• the term $I_a(\ce{A})-E_a(\ce{B})$ characterises the energy required to form isolated ions $\ce{A^+}$ and $\ce{B^-}$ in the gas phase;
• $-e^2/r$ takes into account culonic attraction between two ions.

It is not intuitive for me why ${b}/{r^n}$ is how it is.

The final term, introduced by Max Born, encompasses the repulsion generated by shells of electrons at either ion.

Of course, such effects cannot be ignored. But I am interested in why is it $b/r^n$. What is the justification? Feel free to provide the rigorous approach, even though it will probably$^{[1]}$ be above my abilities of comprehension.

Browsing on Wikipedia, the information might be given in the book Advanced Inorganic Chemistry by F. Albert Cotton, Geoffrey Wilkinson, Carlos A. Murillo, and Manfred Bochmann.

The pertinent section “1-6. Energetics of Ionic Crystals” starts at page 18$^{[2]}$, however I cannot find the derivation. There is only that the value of $n$ relies on a compressibility measurement, given as fractional change in volume per unit change in pressure, or

$$\frac{\Delta V}{V\Delta P}.$$

Also, this is seems somewhat contradictory to the earlier assumption of rigid spheres as written in another book$^{[3]}$. So, if anything, the linked book confused me further.

$^{[1]}$ Most certainly.

$^{[2]}$ Page 28 in the PDF.

$^{[3]}$ U. Palm, V. Past. Physical Chemistry. (1974) [To my knowledge, not available in English.]