What does it mean when the $1s$ and $2s$ orbitals overlap

atomic-physicselectronsenergyorbitalsquantum mechanics

The shape of the $s$ orbital is spherical. Consequently the $1s$ orbital will be a sphere with nucleus as its center while $2s$ will be a similar but bigger sphere.

Now orbitals represent the space in which the electron could be found. But we see that the spaces of $1s$ and $2s$ overlap. So does that mean that a $1s$ and $2s$ electron could be potentially found at the same energy level i.e. at the same distance from the nucleus? There is also a possibility that the 1s electron could lie further from the nucleus than the $2s$ electron. How do we know, in this case, that the $1s$ and $2s$ electron have different energies?

Best Answer

It means that the theoretical explanation that you are being given in chemistry is incomplete. I wouldn't call it false because it is a very useful approximation that explains pretty much everything that we need in entry level chemistry "well enough" (even quantitatively), but it's just not how quantum mechanics of many-particle systems actually works. Let's try to clarify what is really happening.

The orbitals that you are used to from the drawings in physics and chemistry books are the single electron wave functions of hydrogen. In classical physics these orbitals would indeed "overlap" for a multi-electron wave function. Quantum mechanics doesn't work that way, though. A multi-particle wave function doesn't live in the same Hilbert space as a single particle wave function. Instead it lives in the product of several such Hilbert spaces, i.e. it is a higher dimensional distribution than the single electron function. For a single electron atom like hydrogen we can write the wave function as ψ(r). For a two electron atom, however, it becomes ψ(r1,r2), i.e. it now depends on six coordinates rather than three. For n-electrons we have to use ψ(r1,r2,⋯,ri), so we need a 3n-dimensional function to represent the system correctly.

That we can draw orbitals for the hydrogen problem is a mere coincidence because the spatial dimensionality of the solution happens to have the same three dimensions as space itself. For two electrons, however, the actual solution of the corresponding Schroedinger equation would live in six dimensions and so on. This can not be visualized easily. In the "orbital approximation" we are replacing this higher dimensional solution with a much more simple product:

ψ(r1,r2,⋯,ri)≈φ1(r1)φ2(r2)⋯φi(ri)

and we further assume that the electrons (described by the φi(ri) functions) behave independently like in a single electron atom. The reason why we are doing this is because the Schroedinger equation for the full 3n dimensional many-body problem can't be solved in closed form. Even the approximation problem is hard, but it can be analyzed sufficiently well to extract important information about atoms other than hydrogen and even molecules.