Series

Atomic structure — the series

3 essays on one idea, from the one that introduces it to the one that assumes the rest.
  1. Where the electron actually is, by radius. The radial probability density of the hydrogen 1s, 2s, 2p states — the chance of finding the electron in a thin shell at each radius, in units of the Bohr radius. 1s is most likely at 1.00 Bohr radii and averages 1.50; 2s is most likely at 5.24 Bohr radii and averages 6.00; 2p is most likely at 4.00 Bohr radii and averages 5.00. Each curve integrates to one, and each has n − l − 1 radial nodes where the electron is never found.

    Where the electron probably is

    The Bohr atom put the electron on a circle of definite radius. What replaced it keeps the radius as the most likely place to find the electron and gives up the circle, the speed and the trajectory entirely.

    part 1 · quantum
  2. Where 4s goes below 3d. The energies of five orbitals of a nucleus of charge 19, solved in a screened Coulomb potential, against how far out the screening extends. Nothing about the ordering is assumed: each level is found by integrating the radial equation outward and bisecting on the energy until the solution has the number of nodes that state is supposed to have, and the same solver returns hydrogen's −1/2n² to 7.3e-12 hartree when the screening is switched off. With no screening the three n = 3 levels would lie on top of one another. With screening they separate, always in the same order — s lowest, then p, then d — because a low angular momentum has no centrifugal barrier keeping it out of the core, so it spends part of its time inside the other electrons where the nuclear charge is unscreened. And at a screening length of 0.41 bohr the 4s level crosses below 3d, which is the fourth row of the periodic table: potassium and calcium put their electrons in 4s before anything goes into 3d, so they are an alkali metal and an alkaline earth rather than the first two transition metals. The model is a caricature — one screening length for every electron, no self-consistency, and no exchange — and it gets the ordering right anyway, which is the argument that the ordering is about penetration and nothing subtler.

    The order the shells fill

    In hydrogen every state with the same principal number has the same energy, and 4s and 3d differ by nothing. In every other atom they do not, and 4s is below 3d — which is why potassium is an alkali metal rather than the first transition metal. The difference is a small piece of probability that an s orbital has inside the innermost shell and a d orbital does not.

    part 2 · quantum
  3. Why it stops falling in. The energy of an electron confined to a region of radius r around a nucleus, as the sum of two terms with different powers: a confinement energy ħ²/2mr² that rises without limit as the region shrinks, and a Coulomb attraction −Ze²/4πε₀r that falls. At Z = 1 the sum is least at 52.92 pm, where it is -13.61 eV. Both numbers are found by searching the drawn curve and both agree with the Bohr radius over Z and minus Z² Rydbergs to a part in a million. Nothing was quantised to get them. The only quantum input is that confining an electron to a region costs kinetic energy, which is the uncertainty relation and nothing more.

    Why an atom is the size it is

    A tenth of a nanometre is not a measured constant of nature but the outcome of a competition: confining an electron costs kinetic energy, and the nucleus pays for confinement with attraction. Minimising the sum gives the number, and changing the masses moves it by four orders of magnitude.

    part 3 · quantum

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