## Tag Archives: Martin Gouterman

### Mathematics and the periodic table

It isn’t surprising that math is involved in the periodic table. Decades before the existence of atoms was shown for sure (Einstein in 1905 on Brownian motion — https://physicsworld.com/a/einsteins-random-walk/) Mendeleev arranged the known elements in a table according to their chemical properties. Math is great at studying and describing structure, and the periodic table is full of it.

What is surprising, is how periodic table structure arises from math that ostensibly has absolutely nothing to do with chemistry.  Here are 3 examples.

The first occurred exactly 60 years ago to the month in grad school.  The instructor was taking a class of budding chemists through the solution of the Schrodinger equation for the hydrogen atom.

Recursion relations are no stranger to the differential equations course, where you learn to (tediously) find them for a polynomial series solution for the differential equation at hand. I never really understood them, but I could use them (like far too much math that I took back then).

So it wasn’t a shock when the QM instructor back then got to them in the course of solving the hydrogen atom (with it’s radially symmetric potential). First the equation had to be expressed in spherical coordinates (r, theta and phi) which made the Laplacian look rather fierce. Then the equation was split into 3, each involving one of r, theta or phi. The easiest to solve was the one involving phi which involved only a complex exponential. But periodic nature of the solution made the magnetic quantum number fall out. Pretty good, but nothing earthshaking.

Recursion relations made their appearance with the solution of the radial and the theta equations. So it was plug and chug time with series solutions and recursion relations so things wouldn’t blow up (or as Dr. Gouterman put it, the electron has to be somewhere, so the wavefunction must be zero at infinity). MEGO (My Eyes Glazed Over) until all of a sudden there were the main quantum number (n) and the azimuthal quantum number (l) coming directly out of the recursions.

When I first realized what was going on, it really hit me. I can still see the room and the people in it (just as people can remember exactly where they were and what they were doing when they heard about 9/11 or (for the oldsters among you) when Kennedy was shot — I was cutting a physiology class in med school). The realization that what I had considered mathematical diddle, in some way was giving us the quantum numbers and the periodic table, and the shape of orbitals, was a glimpse of incredible and unseen power. For me it was like seeing the face of God.

The second and third examples occurred this year as I was going through Tony Zee’s book “Group Theory in a Nutshell for Physicists”

The second example occurs with the rotation group in 3 dimensions, which is a 3 x 3 invertible matrix, such that multiplying it by its transpose gives the identity, and such that is determinant is +1.  It is called SO(3)

Then he tensors 2 rotation matrices together to get a 9 x 9 matrix.  Zee than looks for the irreducible matrices of which it is composed and finds that there is a 3×3, a 1×1 and a 5×5.  The 5×5 matrix is both traceless and symmetric.  Note that 5 = 2(2) + 1.  If you tensor 3 of them together you get (among other things 3(2) + 1)   = 7;   a 7 x 7 matrix.

If you’re a chemist this is beginning to look like the famous 2 L + 1 formula for the number of the number of magnetic quantum numbers given an orbital quantum number of L.   The application of a magnetic field to an atom causes the orbital momentum L to split in 2L + 1 magnetic eigenvalues.    And you get this from the dimension of a particular irreducible representation from a group.  Incredible.  How did abstract math know this.

The third example also occurs a bit farther along in Zee’s book, starting with the basis vectors (Jx, Jy, Jz) of the Lie algebra of the rotation group SO(3).   These are then combined to form J+ and J-, which raise and lower the eigenvalues of Jz.  A fairly long way from chemistry you might think.

All state vectors in quantum mechanics have absolute value +1 in Hilbert space, this means the eigenvectors must be normalized to one using complex constants.  Simply by assuming that the number of eigenvalues is finite, there must be a highest one (call it j) . This leads to a recursion relation for the normalization constants, and you wind up with the fact that they are all complex integers.  You get the simple equation s = 2j where s is a positive integer.  The 2j + 1 formula arises again, but that isn’t what is so marvelous.

j doesn’t have to be an integer.  It could be 1/2, purely by the math.  The 1/2 gives 2 (1/2) + 1 e.g two numbers.  These turn out to be the spin quantum numbers for the electron.  Something completely out of left field, and yet purely mathematical in origin. It wasn’t introduced until 1924 by Pauli — long after the math had been worked out.

Incredible.

### Ring currents ride again

One of the most impressive pieces of evidence (to me at least) that we really understand what electrons are doing in organic molecules are the ring currents. Recall that the pi electrons in benzene are delocalized above and below the planar ring determined by the 6 carbon atoms.

How do we know this? When a magnetic field is applied the electrons in the ring cloud circulate to oppose the field. So what? Well if you can place a C – H bond above the ring, the induced current will shield it. Such molecules are known, and the new edition of Clayden (p. 278) shows the NMR spectra showing [ 7 ] paracyclophane which is benzene with 7 CH2’s linked to the 1 and 4 positions of benzene, so that the hydrogens of the 4th CH2 is directly over the ring (7 CH2’s aren’t long enough for it to be anywhere else). Similarly, [ 18 ] Annulene has 6 hydrogens inside the armoatic ring — and these hydrogens are even more deshielded. Interestingly building larger and larger annulenes, as shown that aromaticity decreases with increasing size, vanishing for systems with more than 30 pi electrons (diameter 13 Angstroms), probably because planarity of the carbons becomes less and less possible, breaking up the cloud.

This brings us to Nature vol. 541 pp. 200 – 203 ’17 which describes a remarkable molecule with 6 porphyins in a ring hooked together by diyne linkers. The diameter of the circle is 24 Angstroms. Benzene and [ 18 ] Annulene have all the carbons in a plane, but the picture of the molecule given in the paper does not. Each of the porphyrins is planar of course, but each plane is tangent to the circle of porphyrins.

Also discussed is the fact that ‘anti-aromatic’ ring currents exist, in which they circulate to enhance rather than diminish the imposed magnetic field. The molecule can be switched between the aromatic and anti-aromatic states by its oxidation level. When it has 78 electrons ( 18 * 4 ) + 2 in the ring (with a charge of + 6) it is aromatic. When it has 80 elections with a + 4 charge it is anti-aromatic — further confirmation of the Huckel rule (as if it was needed).

On a historical note reference #27 is to a paper of Marty Gouterman in 1961, who was teaching grad students in chemistry in the spring of 1961. He was an excellent teacher. Here he is at the University of Washington — http://faculty.washington.edu/goutermn/