A small puzzle I recently set for myself was finding out how the hydrogenic orbital eigenstates give rise to the S- P- D- and F- orbitals in chemistry (and where s, p, d and f came from).
The reason this puzzle is important to me is that many of my interests sort of straddle how to go from the angstrom scale to the nanometer scale. There is a cross-over where physics becomes chemistry, but chemists and physicists often look at things very differently. I was not directly trained as a P-chemist; I was trained separately as a Biochemist and a Physicist. Remarkably, the Venn diagrams describing the education for these pursuits only overlap slightly. When Biochemists and Molecular Biologists talk, the basic structures below that are frequently just assumed (the scale here is >1nm), while Physicists frequently tend to focus their efforts toward going more and more basic (the scale here is <1 Angstrom). This leads to a clear non-overlap in the scale where chemistry and P-chem are relevant (~1 angstrom). Quite ironically, the whole periodic table of the elements lies there. I have been through P-chem and I’ve gotten hit with it as a Chemist, but this is something of an inconvenient scale gap for me. So, a cat’s paw of mine has been understanding, and I mean really understanding, where quantum mechanics transitions to chemistry.
One place is understanding how to get from the eigenstates I know how to solve to the orbitals structuring the periodic table.
This assemblage is pure quantum mechanics. You learn a huge amount about this in your quantum class. But, there are some fine details which can be left on the counter.
One of those details for me was the discrepancy between the hydrogenic wave functions and the orbitals on the periodic table. If you aren’t paying attention, you may not even know that the s-, p-, d- orbitals are not all directly the hydrogenic eigenstates (or perhaps you were paying a bit closer attention in class than I was and didn’t miss when this detail was brought up). The discrepancy is a very subtle one because often times when you start looking for images of the orbitals, the sources tend to freely mix superpositions of eigenstates with direct eigenstates without telling why the mixtures were chosen…
For example, here are the S, P and D orbitals for the periodic table:
This image is from http://www.chemcomp.com. Focusing on the P row, how is it that these functions relate to the pure eigenstates? Recall the images that I posted previously of the P eigenstates:
In the image for the S, P and D orbitals, of the Px, Py and Pz orbitals, all three look like some variant of P210, which is the pure state on the left, rather than P21-1, which is the state on the right. In chemistry, you get the orbitals directly without really being told where they came from, while in physics, you get the eigenstates and are told somewhat abstractly that the s-, p-, d- orbitals are all superpositions of these eigenstates. I recall seeing a professor during an undergraduate quantum class briefly derive Px and Py, but I really didn’t understand why he selected the combinations he did! Rationally, it makes sense that Pz is identical to P210 and that Px and Py are superpositions that have the same probability distribution as Pz, but are rotated into the X-Y plane ninety degrees from one another. How do Px and Py arise from superpositions of P21-1 and P211? P21-1 and P211 have identical probability distributions despite having opposite angular momentum!
Admittedly, the intuitive rotations that produce Px and Py from Pz make sense at a qualitative level, but if you try to extend that qualitative understanding to the D-row, you’re going to fail. Four of the D orbitals look like rotations of one another, but one doesn’t. Why? And why are there four that look identical? I mean, there are only three spatial dimensions to fill, presumably. How do these five fit together three dimensionally?
Except for the Dz^2, none of the D-orbitals are pure eigenstates: they’re all superpositions. But what logic produces them? What is the common construction algorithm which unites the logic of the D-orbitals with that of the P-orbitals (which are all intuitive rotations).
I’ll actually hold back on the math in this case because it turns out that there is a simple revelation which can give you the jump.
As it turns out, all of chemistry is dependent on angular momentum. When I say all, I really do mean it. The stability of chemical structures is dependent on cases where angular momentum has tended in some way to cancel out. Chemical reactivity in organic chemistry arises from valence choices that form bonds between atoms in order to “complete an octet,” which is short-hand for saying that species combine with each other in such a way that enough electrons are present to fill in or empty out eight orbitals (roughly push the number of electrons orbiting one type of atom across the periodic table in its appropriate row to match the noble gases column). For example, in forming the salt crystal sodium chloride, sodium possesses only one electron in its valence shell while chlorine contains seven: if sodium gives up one electron, it goes to a state with no need to complete the octet (with the equivalent electronic completion of neon), while chlorine gaining an electron pushes it into a state that is electronically equal to argon, with eight electrons. From a physicist stand-point, this is called “angular momentum closure,” where the filled orbitals are sufficient to completely cancel out all angular momentum in that valence level. As another example, one highly reactive chemical structure you might have heard about is a “radical” or maybe a “free radical,” which is simply chemist shorthand for the situation a physicist would recognize contains an electron with uncancelled spin and orbital angular momentum. Radical driven chemical reactions are about passing around this angular momentum! Overall, reactions tend to be driven to occur by the need to cancel out angular momentum. Atomic stoichiometry of a molecular species always revolves around angular momentum closure –you may not see it in basic chemistry, but this determines how many of each atom can be connected, in most cases.
From the physics, what can be known about an orbital is essentially the total angular momentum present and what amount of that angular momentum is in a particular direction, namely along the Z-axis. Angular momentum lost in the X-Y plane is, by definition, not in either the X or Y direction, but in some superposition of both. Without preparing a packet of angular momentum, the distribution ends up having to be uniform, meaning that it is in no particular direction except not in the Z-direction. For the P-orbitals, the eigenstates are purely either all angular momentum in the Z-direction, or none in that direction. For the D-orbitals, the states (of which there are five) can be combinations, two with angular momentum all along Z, two with half in the X-Y plane and half along Z and one with all in the X-Y plane.
What I’ve learned is that, for chemically relevant orbitals, the general rule is “minimal definite angular momentum.” What I mean by this is that you want to minimize situations where the orbital angular momentum is in a particular direction. The orbits present on the periodic table are states which have canceled out angular momentum located along the Z-axis. This is somewhat obvious for the homology between P210 and Pz. P210 points all of its angular momentum perpendicular to the z-axis. It locates the electron on average somewhere along the Z-axis in a pair of lobes shaped like a peanut, but the orbital direction is undefined. You can’t tell how the electron goes around.
As it turns out, Px and Py can both be obtained by making simple superpositions of P21-1 and P211 that cancel out z-axis angular momentum… literally adding together these two states so that their angular momentum along the z-axis goes away. Px is the symmetric superposition while Py is the antisymmetric version. For the two states obtained by this method, if you look for the expectation value of the z-axis angular momentum, you’ll find it missing! It cancels to zero.
It’s as simple as that.
The D-orbitals all follow. D320 already has no angular momentum on the z-axis, so it is directly Dzz. You therefore find four additional combinations by simply adding states that cancel the z-axis angular momentum: D321 and D32-1 symmetric and antisymmetric combinations and then the symmetric and antisymmetric combinations of D322 and D32-2.
Notice, all I’m doing to make any of these states is by looking at the last index (the m-index) of the eignstates and making a linear combination where the first index plus the second gives zero. 1-1 =0, 2-2=0. That’s it. Admittedly, the symmetric combination sums these with a (+) sign and a 1/sqrt(2) weighting constant so that Px = (1/sqrt(2))(P21 + P21-1) is normalized and the antisymmetric combination sums with a (-) sign as in Py = (1/sqrt(2))(P211 – P21-1), but nothing more complicated than that! The D-orbitals can be generated in exactly the same manner. I found one easy reference on line that loosely corroborated this observation, but said it instead as that the periodic table orbitals are all written such that the wave functions have no complex parts… which is also kind of true, but somewhat misleading because you sometimes have to multiply by a complex phase to put it genuinely in the form of sines for the polar coordinate (and as the polar coordinate is integrated over 360 degrees, expectation values on this coordinate, as z-axis momentum would contain, cancel themselves out; sines and cosines integrated over a full period, or multiples of a full period, integrate to zero.)
Before I wrap up, I had a quick intent to touch on where S-, P-, D- and F- came from. “Why did they pick those damn letters?” I wondered one day. Why not A-, B-, C- and D-? The nomenclature emerged from how spectral lines appeared visually and groups were named: (S)harp, (P)rincipal, (D)iffuse and (F)undamental. (A second interesting bit of “why the hell???” nomenclature is the X-ray lines… you may hate this notation as much as me: K, L, M, N, O… “stupid machine uses the K-line… what does that mean?” These letters simply match the n quantum number –the energy level– as n=1,2,3,4,5… Carbon K-edge, for instance, is the amount of energy between the n=1 orbital level and the ionized continuum for a carbon atom.) The sharpness tends to reflect the complexity of the structure in these groups.
As a quick summary about structuring of the periodic table, S-, P-, D-, and F- group the vertical columns (while the horizontal rows are the associated relative energy, but not necessarily the n-number). The element is determined by the number of protons present in the nucleus, which creates the chemical character of the atom by requiring an equal number of electrons present to cancel out the total positive charge of the nucleus. Electrons, as fermions, are forced to occupy distinct orbital states, meaning that each electron has a distinct orbit from every other (fudging for the antisymmetry of the wave function containing them all). As electrons are added to cancel protons, they fall into the available orbitals depicted in the order on the periodic table going from left to right, which can be a little confusing because they don’t necessarily purely close one level of n before starting to fill S-orbitals of the next level of n; for example at n=3, l can equal 0, 1 and 2… but, the S-orbitals for n=4 will fill before D-orbitals for n=3 (which are found in row 4). This has purely to do with the S-orbitals having lower energy than P-orbitals which have lower energy than D-orbitals, but that the energy of an S-orbital for a higher n may have lower energy than the D-orbital for n-1, meaning that the levels fill by order of energy and not necessarily by order to angular momentum closure, even though angular momentum closure influences the chemistry. S-, P-, D-, and F- all have double degeneracy to contain up and down spin of each orbital, so that S- contains 2 instead of 1, P- contains 6 instead of 3, and D- from 10 instead of 5. If you start to count, you’ll see that this produces the numerics of the periodic table.
Periodic table is a fascinating construct: it contains a huge amount of quantum mechanical information which really doesn’t look much like quantum mechanics. And, everybody has seen the thing! An interesting test to see the depth of a conversation about periodic table is to ask those conversing if they understand why the word “periodic” is used in the name “Periodic table of the elements.” The choice of that word is pure quantum mechanics.
Here’s an interesting aside.
If you look at that image above that contains the S, P and D orbitals, you’ll note that the P orbitals are annotated as Px, Py and Pz, while the D orbitals are Dxy, Dxz, Dyz and so on.
For the P orbitals, the x, y and z are the cartesian forms of the spherical harmonics that produce the given orbital. For the D orbitals, the combinations, xy and so on, are also the spherical harmonics that produce the orbital. Note, x is a linear combination of Y11 and Y1-1… undoing the linear combination produces x!