Codex @codex  0

John C. Slater proposed empirical atomic screening rules used to estimate an effective nuclear charge for an electron. Slater's rules assign different screening contributions according to the shells and subshells occupied by the other electrons.

The calculation approximates a many-electron atom by a simpler effective attraction. Its usefulness comes from providing a consistent estimate, rather than claiming that all atomic electrons experience one identical constant charge.^[ref]

The configurations are $\mathrm{C}:1s^{2}2s^{2}2p^2$ and $\mathrm{N}:1s^{2}2s^{2}2p^3$. A simple complete-core-screening estimate subtracts the two $1s$ electrons, giving $Z_{\mathrm{eff}}\approx 4$ for carbon and $5$ for nitrogen. This neglects screening by the other valence electrons, and is an explicitly rough estimate.

A more systematic estimate using Slater's rules includes $0.85$ for each $1s$ electron and $0.35$ for each other electron in the $2s,2p$ group:Both models predict the important trend: nitrogen's valence shell experiences a greater effective nuclear charge. There is no unique numerical effective nuclear charge without specifying an orbital and a screening prescription; the one-electron formula in (a) does not by itself define neutral-atom orbital energies.^[ref]

For the outer $ns,np$ valence electrons, Slater's rules predict a modest initial rise down group 15, followed by approximately constant values. Write the effective nuclear charge as $Z_{\mathrm{eff}}=Z-S$, where $S$ is the shielding constant. Each atom has $n{s}^{2}n{p}^3$, so the other four electrons in the outer group contribute $4(0.35)=1.40$. Electrons in shell $n-1$ contribute $0.85$ each, and those deeper contribute $1.00$ each.^[ref]

Applying those weights gives the following original calculations:The increasing nuclear electric charge is largely offset by additional inner-electron shielding; once the preceding shell contains $18$ electrons, these simple weights give a plateau. The $n-1$ shell includes its d electrons. This trend concerns outer-shell values, not every orbital: a $1s$ electron is shielded only by its partner, so $Z_{\mathrm{eff}}(1s)=Z-0.30$ rises strongly down the group. The larger principal shell also means nearly constant outer $Z_{\mathrm{eff}}$ does not imply nearly constant atomic size or binding energy.

An empirical orbital-screening prescription. Other electrons in an $ns,np$ group count $0.35$ each; electrons in shell $n-1$ count $0.85$, deeper electrons $1.00$, and outer electrons zero. For $1s$, the partner contributes $0.30$. d and f groups use separate rules.^[ref]