Why is the 2s orbital lower in energy than the 2p orbital when the electrons in 2s are
usually farther from the nucleus?
(Dated: September 29, 2016)
From chemistry.stackexchange.com
/questions/152/why-is-the-2s-orbital-lower-in-energy-
than-the-2p-orbital-whenthe-electrons-in
I. QUESTION
My chemistry book explains that even though elec-
trons in the 2p orbital are closer to the nucleus on av-
erage, electrons from the 2s orbital spend a very short
time very close to the nucleus (penetration), so it has a
lower energy. Why does this tiny amount of time spent
close to the nucleus make such a big difference? It seems
like it should be the average distance that matters, not
the smallest distance achieved at any one point, in de-
termining stability. What makes that momentary drop
in energy so important that it is outweighs all the time
spent farther away from the nucleus with a higher en-
ergy?
II. ANSWER 1
I think your question implicates another question
(which is also mentioned in some comments here),
namely: Why are all energy eigenvalues of states with
a different angular momentum quantum number ℓ but
with the same principal quantum number n (e.g. 3s, 3p,
3d) degenerate in the hydrogen atom but non-degenerate
in multi-electron atoms? Although AcidFlask already
gave a good answer (mostly on the non-degeneracy part)
I will try to eleborate on it from my point of view and
give some additional information. I will split my answer
in three parts: The first will address the ℓ- degeneracy
in the hydrogen atom, in the second I will try to explain
why this degeneracy is lifted, and in the third I will
try to reason why 3s states are lower in energy than 3p
states (which are in turn lower in energy than 3d states).
1. ℓ-degeneracy of the hydrogen atoms energy
eigenvalues
The non-relativistic electron in a hydrogen atom
experiences a potential that is analogous to the Kepler
problem known from classical mechanics. This potential
(aka Kepler potential) has the form κr , where r is the
distance between the nucleus and the electron, and κ is a
proportionality constant. Now, it is known from physics
that symmetries of a system lead to conserved quantities
(Noether Theorem). For example from the rotational
symmetry of the Kepler potential follows the conserva-
tion of the angular momentum, which is characterized
by ℓ. But while the length of the angular momentum
vector is fixed by ℓ there are still different possibilities
for the orientation of its z-component, characterized
by the magnetic quantum number m, which are all
energetically equivalent as long as the system maintains
its rotational symmetry. So, the rotational symmetry
leads to the m-degeneracy of the energy eigenvalues
for the hydrogen atom. Analogously, the ℓ-degeneracy
of the hydrogen atoms 1/6 energy eigenvalues can also
be traced back to a symmetry, the SO(4) symmetry.
The system’s SO(4) symmetry is not a geometric
symmetry like the one explored before but a so called
dynamical symmetry which follows from the form of
the Schroedinger equation for the Kepler potential. (It
corresponds to rotations in a four-dimensional cartesian
space. Note that these rotations do not operate in some
physical space.) This dynamical symmetry conserves
the Laplace-Runge-Lenz vector M ⃗ˆ and it can be shown
that this conserved quantity leads to the ℓ-independent
energy spectrum with E ∝ n12 . (A detailed derivation,
though in German, can be found here.)
2. Why is the ℓ-degeneracy of the energy eigenvalues
lifted in multielectron atoms?
As the m-degeneracy of the hydrogen atom’s energy
eigenvalues can be broken by destroying the system’s
spherical symmetry, e.g. by applying a magnetic field,
the ℓ degeneracy is lifted as soon as the potential

appearing in the Hamilton operator deviates from the
pure κr form. This is certainly the case for multielectron
atoms since the outer electrons are screened from the
nuclear Coulomb attraction by the inner electrons and
the strength of the screening depends on their distance
from the nucleus. (Other factors, like spin and relativis-
tic effects, also lead to a lifting of the ℓ-degeneracy even
in the hydrogen atom.)
3. Why do states with the same n but lower ℓ values
have lower energy eigenvalues?
Two effects are important here: The centrifugal force
puts an ”energy penalty” onto states with higher angu-
lar momentum.1 So, a higher ℓ value implies a stronger
centrifugal force, that pushes electrons away from the nu-
cleus. 1. The concept of centrifugal force can be seen in
the radial Schroedinger equation for the radial part R(r)
of the wave function Ψ(r, θ, φ) = R(r)Yℓ,m (θ, φ)
( 2 2 ) be closer to the nucleus than those in the s orbits, i.e.
−~ d ~2 ℓ(ℓ + 1) Ze2
+ − − E rR(r) = 0 (1)
2me dr2 2m r2 2me r
| e {z } electrons do not actually have classical orbits and that
ℓ
= Vcf (r)
(2)
The radial part experiences an additional ℓ-dependent
potential Vcfℓ (r) that pushes the electrons away from the
nucleus. Core repulsion (Pauli repulsion), on the other
hand, puts an ”energy penalty” on states with a lower
angular momentum. That is because the core repulsion
acts only between electrons with the same angular
momentum1 . So it acts stronger on the low-angular
momentum states since there are more core shells with
lower angular momentum.
1. Core repulsion is due to the condition that the
wave functions must be orthogonal which in turn is a
consequence of the Pauli principle. Because states with
different ℓ values are already orthogonal by their angular
motion, there is no Pauli repulsion between those states.
However, states with the same ℓ value feel an additional
effect from core orthogonalization.
The ”accidental” ℓ-degeneracy of the hydrogen atom
can be described as a balance between centrifugal force
and core repulsion, that both act against the nuclear
Coulomb attraction. In the real atom the balance
between centrifugal force and core repulsion is broken,
The core electrons are contracted compared to the outer
electrons because there are less inner electron-shells
screening the nuclear attraction from the core shells
than from the valence electrons. Since the inner electron
shells are more contracted than the outer ones, the core
repulsion is weakened whereas the effects due to the
centrifugal force remain unchanged. The reduced core
repulsion in turn stabilizes the states with lower angular
2
momenta, i.e. lower ℓ values. So, 3s states are lower in
energy than 3p states which are in turn lower in energy
than 3d states.
III. ANSWER 2
General chemistry textbooks tend to explain atomic
structure exceedingly poorly using a hodgepodge of
obsolete concepts. Your chemistry book provides such a
typical example - the notion of penetration only makes
sense in the ancient Bohr-Sommerfeld model that has
been obsolete since the discovery of quantum mechanics!
The idea was that orbits of electrons in p states were
more elliptical than those in s states because they had
more angular momentum, and so on average there will
be some fraction of the time where p electrons would
they would penetrate the s orbit. We now know that
the Bohr-Sommerfeld model is wrong. However there
remains one correct statement of fact, which is that
electrons in p orbitals by definition have more angular
momentum than those in s orbitals. (The orbital angular
momentum is l = 1 in p and l = 0 in s.) Nonetheless it is
completely misleading, since 2s and 2p orbitals are only
well-defined in hydrogen and other ions with only one
electron, and furthermore that all orbitals of the same
principal quantum number are degenerate in energy in
hydrogenic systems. Thus angular momentum alone
cannot be the answer. It is only due to electron-electron
interactions that the orbitals that correspond to 2s and
2p in multielectron atoms split and become nondegen-
erate. The effect of having more angular momentum
therefore turns out to be only indirectly responsible
via the different many-electron interactions occurring
in the analogs of 2p and 2s orbitals in many-electron
atoms. The simplest explanation that is even remotely
correct is the screening effect, where the 2s electrons by
their very presence make the 2p electrons feel a lower
effective nuclear charge than if they were absent. A more
precise quantum mechanical statement is that Slater’s
variational treatment of the nuclear charge in hydrogenic
orbitals results in a lower effective nuclear charge for
2p electrons than 2s orbitals. There is unfortunately
no good a priori physical principle for this; it is merely
a statement of a result from a quantum mechanical
calculation. Summary: 2p electrons are higher in energy
than 2s ones due to screening effects that result from
electron-electron interactions. Explanations involving
penetration of classical orbits or purely angular momen-
tum considerations are wrong, even though they tend to
show up in general chemistry textbooks.

IV. ANSWER 3
It is the average energy that matters. Note that this
stuff about ”spends so much time here and so
much there...” is really just a (not particularly
good) way of describing a quantum-mechanical
wave function’s absolute square. The electron
is actually never at any particular place in the
orbital, rather it’s everywhere at the same time
until you decide to measure its precise position
(thereby destroying the orbital, that has to do with
the Heisenberg uncertainty principle), in which
case there would be a certain probability of find-
ing it here or there. That probability can be cal-
culated from the wave function φ(x)by taking its
absolute square, which gives the radial distribu-
tion function in your plots.
The energy of any quantum state is determined by
3
the expectation value of the Hamiltonian operator, which
very roughly means ”measure the energy at all places in
space, multiply with the probability the electron is found
at that place, and add all those values up”. That should
sound quite intuitive. In actuality it’s more complicated:
the electron also has some kinetic energy at every place
in space, which is itself encoded in the wave function but
you need to consider its complex phase, which is a whole
extra dimension that you simply don’t see in your plots
and certainly not in the average distance.
Calculating the exact energies for atomic orbitals is a
lot of maths that probably doesn’t belong here, but it’s
possible to carry it out*, and it should be obvious now
that the result doesn’t necessarily have much to do with
simple ”energy at the average distance”. The quantities
such as angular momentum mentioned in CHM’s answer
can be used to make it a bit simpler again (the Hamilto-
nian separates into a radial and spherical part), but that
alone doesn’t really explain much I suppose.