Friday, March 29, 2019

Proving the Periodic Table

The year 2019 is the International Year of the Periodic Table celebrating the 150th anniversary of Mendeleev's discovery. This prompts me to report on something that I learned in recent years when co-teaching "Mathematical Quantum Mechanics" with mathematicians in particular with Heinz Siedentop: We know less about the mathematics of the periodic table) than I thought.



In high school chemistry you learned that the periodic table comes about because of the orbitals in atoms. There is Hundt's rule that tells you the order in which you have to fill the shells in and in them the orbitals (s, p, d, f, ...). Then, in your second semester in university, you learn to derive those using Sehr\"odinger's equation: You diagonalise the Hamiltonian of the hyrdrogen atom and find the shells in terms of the main quantum number $n$ and the orbitals in terms of the angular momentum quantum number $L$ as $L=0$ corresponds to s, $L=1$ to p and so on. And you fill the orbitals thanks to the Pauli excursion principle. So, this proves the story of the chemists.

Except that it doesn't: This is only true for the hydrogen atom. But the Hamiltonian for an atom nuclear charge $Z$ and $N$ electrons (so we allow for ions) is (in convenient units)
$$ a^2+b^2=c^2$$

$$ H = -\sum_{i=1}^N \Delta_i -\sum_{i=1}^N \frac{Z}{|x_i|} + \sum_{i\lt j}^N\frac{1}{|x_i-x_j|}.$$

The story of the previous paragraph would be true if the last term, the Coulomb interaction between the electrons would not be there. In that case, there is no interaction between the electrons and we could solve a hydrogen type problem for each electron separately and then anti-symmetrise wave functions in the end in a Slater determinant to take into account their Fermionic nature. But of course, in the real world, the Coulomb interaction is there and it contributes like $N^2$ to the energy, so it is of the same order (for almost neutral atoms) like the $ZN$ of the electron-nucleon potential.

The approximation of dropping the electron-electron Coulomb interaction is well known in condensed matter systems where there resulting theory is known as a "Fermi gas". There it gives you band structure (which is then used to explain how a transistor works)


Band structure in a NPN-transistor
Also in that case, you pretend there is only one electron in the world that feels the periodic electric potential created by the nuclei and all the other electrons which don't show up anymore in the wave function but only as charge density.

For atoms you could try to make a similar story by taking the inner electrons into account by saying that the most important effect of the ee-Coulomb interaction is to shield the potential of the nucleus thereby making the effective $Z$ for the outer electrons smaller. This picture would of course be true if there were no correlations between the electrons and all the inner electrons are spherically symmetric in their distribution around the nucleus and much closer to the nucleus than the outer ones.  But this sounds more like a day dream than a controlled approximation.

In the condensed matter situation, the standing for the Fermi gas is much better as there you could invoke renormalisation group arguments as the conductivities you are interested in are long wave length compared to the lattice structure, so we are in the infra red limit and the Coulomb interaction is indeed an irrelevant term in more than one euclidean dimension (and yes, in 1D, the Fermi gas is not the whole story, there is the Luttinger liquid as well).

But for atoms, I don't see how you would invoke such RG arguments.

So what can you do (with regards to actually proving the periodic table)? In our class, we teach how Lieb and Simons showed that in the $N=Z\to \infty$ limit (which in some sense can also be viewed as the semi-classical limit when you bring in $\hbar$ again) that the ground state energy $E^Q$ of the Hamiltonian above is in fact approximated by the ground state energy $E^{TF}$ of the Thomas-Fermi model (the simplest of all density functional theories, where instead of the multi-particle wave function you only use the one-particle electronic density $\rho(x)$ and approximate the kinetic energy by a term like $\int \rho^{5/3}$ which is exact for the three fermi gas in empty space):

$$E^Q(Z) = E^{TF}(Z) + O(Z^2)$$

where by a simple scaling argument $E^{TF}(Z) \sim Z^{7/3}$. More recently, people have computed more terms in these asymptotic which goes in terms of $Z^{-1/3}$, the second term ($O(Z^{6/3})= O(Z^2)$ is known and people have put a lot of effort into $O(Z^{5/3})$ but it should be clear that this technology is still very very far from proving anything "periodic" which would be $O(Z^0)$. So don't hold your breath hoping to find the periodic table from this approach.

On the other hand, chemistry of the periodic table (where the column is supposed to predict chemical properties of the atom expressed in terms of the orbitals of the "valence electrons") works best for small atoms. So, another sensible limit appears to be to keep $N$ small and fixed and only send $Z\to\infty$. Of course this is not really describing atoms but rather highly charged ions.

The advantage of this approach is that in the above Hamiltonian, you can absorb the $Z$ of the electron-nucleon interaction into a rescaling of $x$ which then let's $Z$ reappear in front of the electron-electron term as $1/Z$. Then in this limit, one can try to treat the ugly unwanted ee-term perturbatively.

Friesecke (from TUM) and collaborators have made impressive progress in this direction and in this limit they could confirm that for $N < 10$ the chemists' picture is actually correct (with some small corrections). There are very nice slides of a seminar talk by Friesecke on these results.

Of course, as a practitioner, this will not surprise you (after all, chemistry works) but it is nice to know that mathematicians can actually prove things in this direction. But it there is still some way to go even 150 years after Mendeleev.

3 comments:

dtvmcdonald said...

150 years after Mendeleev we chemists know perfectly well about how the Periodic Table actually works. We don't need modern physicists' hand-wavings, mid 20th century chemists already reached the pinnacle of the utility of hand-waving.

The periodic table is explained first by the fact that yes, the Born-Oppenheimer approximation is really very good: interatomic potentials explain most of atomic motions, and is very good for thermodynamics. Second, up to roughly Bromine the Schrodinger Equation works to calculate those potentials, assuming you get a near-exact solution.

Above Bromine the Schrodinger Equation slowly stops working, and at Iodine its essentially useless. For closed shells you can fake relativistic effects using "canned" fake wave functions. For open shells you must start with the Dirac equation. Of course in reality the Dirac equation is "wrong" as one should treat electron-electron repulsion using relavistic field theory, but as far as I know
no one has yet done that, perhaps I'm behind the times.

In my grad school days we saw strange stereochemisty with iodine, that was explained only years later with very very complicated relativistic electronic structure effects.

Of course, some chemistry does involve Born-Oppenheimer breakdown, a whole different field of approximation than yours.

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Marysia said...


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