Why is a 3s orbital lower in energy than a 3p orbital in all atoms other than a hydrogen atom which only has a single electron?

1 Answer
Mar 15, 2017

Because of how there IS only one electron in "H" atom. That single electron does not introduce orbital anguar momentum, so no matter what value of l, the orbital energies for the same n are all the same.


The added electrons in multi-electron atoms are intrinsically correlated in such a way that each electron is influenced by the motions of the others.

This electron correlation introduces the effect of electron-electron repulsion. That in turn generates an energy splitting of the orbitals with the same n but different l.

For example, for just the 3s and 3p...

"H" atom:

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" "" "" "underbrace(" "" "" "" "" "" "" "" "" ")
3s" "" "" "" "" "" "3p

For multi-electron atoms:

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" "" "" "underbrace(" "" "" "" "" "" "" "" "" ")
ul(color(white)(uarr darr))" "" "" "" "" "3p
3s

We had that the 3s, 3p, 3d orbitals are the same energy in the "H" atom, but in higher-electron atoms, we instead have the energy ordering 3s < 3p < 3d.

In multi-electron atoms, higher l is higher energy for orbitals with the same n.