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:

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

For multi-electron atoms:

#" "" "" "ul(color(white)(uarr darr))" "ul(color(white)(uarr darr))" "ul(color(white)(uarr darr))"#
#" "" "" "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#.