bhobba said:
It means when bound to an atom you can't really consider it as separate particles - you have to consider it as a system because they are entangled.
I agree you can't consider the electrons separately from the rest of the atom, it's a bound system. What I'm doing is further adding that you also can't consider "the electrons in the atom" separately from the electrons in the rest of the universe, because that would be to imply they are distinguishable, and they are not. Of course in practice we do allow ourselves, though formally incorrectly, to use the language "the electrons in the atom", as long as we realize we really mean "whatever electrons show up in our measurement on the atom". They could be any electrons in the universe, and indeed quantum mechanics is quite explicit on this point, that's why the "total wave function" of the universe (if you are the type to believe there is meaning in such a thing, which Brian Cox clearly is) does not say which electrons are in that atom and which electrons aren't. The identity of the electrons in the atom never appears anywhere in the wavefunction of the universe, and importantly so-- that's where the PEP comes from. Granted, the PEP really only cares about electrons with overlapping wavefunctions, but here we are in Brian Cox-land where there is just one wavefunction for the whole universe, which contains all the information in the universe, and since that wavefunction lacks information about the identity of the electrons in that atom, there is, in formal quantum mechanics, no such thing as "the electrons in that atom." Of course this only matters for the tiniest of correlations, but that's what this thread is all about.
The reason electrons can't be in the same state is if electron 1 is in state |u1> and electron 2 in state |u2> the composite system is |u1>|u2>. If |u1> and |u2> are the same state then nothing happens on exchange in contradiction to the fact it must change sign. BUT if bound to an atom its entangled with the nucleus and you can't specify the state of the electron by itself and the argument breaks down. You must consider it as a whole and when that is done it could be a fermion on boson.
All the same, atoms have the structure they have because of the PEP. The entanglements with the nucleus do not change that, though I admit I've never thought about how it might subtly alter the structure of an atom to think about entanglements and not just interaction energies and exchange terms. Has anyone?
Added Later:
I think I may see Kens point. Yes, even in bound atoms you can't tell the difference between electrons. What I am saying is, even though that's still true, the consequences are different - it doesn't necessarily lead to they can't be in the same state.
But it generally does-- we have the level structure of atoms as a result. I presume you are talking about tiny deviations from the simple application of the PEP to electron states that are unentangled with the nucleus, and I've never even thought about those possible repercussions, though we know they have to be small. So I've not disputed your point about entanglements, it was the language about an atom taking its electrons with it that can't be right because "the atom's electrons" is not a formally correct concept. Instead, what the atom "takes with it" are the coordinates of whatever measurement we are doing on the atom, not "its electrons," because the latter require distinguishing that which cannot, by any experiment, be distinguished.
So I'm saying that formally, if we are being more precise than is generally necessary, all we can say is that the total wavefunction of all the electrons in the universe must contain aspects that guarantee we'll usually find some N electrons in that atom if we look. Entanglements with the nucleus, and the interaction energies, are what ensure that, but they are still buried in the evolution of the total wavefunction in ways that does not allow the electrons in that atom to be formally recognized as individual entities, and there's always some probability they will tunnel out of the atom and exchange with other electrons that tunnel in. Not only can no observation rule that out, occasionally we find an observation that
requires it. The rest of the time, we'd be nuts to try to take that into account, and a lot of what we do in quantum mechanics is actually a "manual" approximation that we know will work. But even if we are being unnecessarily precise, we agree the universal wavefunction does not propagate signals halfway across the universe. But it certainly could swap electrons halfway across the universe, and not only couldn't we tell the difference, it is one of the central tenets of quantum mechanics that we couldn't tell the difference.