Concept

Atomic structure — where it appears

The arrangement of electrons around a nucleus, and the rules that decide which arrangements are allowed and what energies they have. Two ingredients settle almost all of it: a wave that has to fit, and an exclusion rule that forbids two electrons the same state.

Named by 6 essays across 2 fields — each of them below, with the objects they name alongside it.

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.

quantum · Atomic structure
The energy ladder of a box. The first 6 energy levels of a box, drawn to scale in E₁, at 1.0, 4.0, 9.0, 16.0, 25.0, 36.0. The levels spread apart as the square of n, so a box's spectrum has no top. The arrow marks a transition: 4 to 3 releases 7.000 E₁.

No two in the same state, and why matter has volume

Nothing in the energy levels of an atom says how many electrons may occupy each one. The answer is one per state, it is not derived from any force, and it is the reason a table holds a cup up.

quantum · Exclusion
The classical atom, and how long it lasts. An electron in a circular orbit of 5.29·10⁻¹¹ m loses energy at the rate the Larmor formula gives, so its radius obeys r³ = r₀³ − 4k²t/c³ and reaches zero in 1.556·10⁻¹¹ seconds — 16 picoseconds. It completes about 2.04·10⁵ orbits on the way, so the spiral is far too tight to draw. Nothing in this calculation is wrong: the acceleration is right, the radiated power is right, and the conclusion is that matter cannot exist. The curve is the shape of that conclusion.

A charge that turns must glow

An accelerating charge radiates, and a charge going round in a circle is accelerating. Apply that to an electron orbiting a nucleus and classical physics predicts that every atom collapses in sixteen picoseconds — a calculation with nothing wrong in it except its conclusion.

astrophysics · Radiating charge
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.

quantum · Atomic structure
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.

quantum · Atomic structure
The half-life that depends on the electrons. Half-lives of 3 nuclides as neutral atoms and as bare nuclei, measured at a heavy-ion storage ring where fully stripped ions can be kept circulating for months. The changes are not corrections. ¹⁸⁷Re goes from 41.6 billion years to 32.9 — a factor of 1.26 billion — because a beta decay whose available energy is only 2.5 keV cannot put an electron into the continuum but can put one into an empty K orbital, and stripping the atom opens that channel. ¹⁶³Dy is stable as an atom and decays in 47 days as a bare nucleus, for the same reason. The rate is a property of the nucleus and of what surrounds it, and the rung below this one says otherwise.

The half-life that chemistry can change

The first rung of this ladder said a nucleus has no clock and that nothing outside it touches the rate. That is very nearly true and it is not exactly true. Electron capture takes an electron from the nucleus's own position, so its rate is proportional to how many electrons are there — which is chemistry, worth a per cent. And a nucleus stripped of every electron can gain a decay channel it did not have: rhenium-187 goes from forty-two billion years to thirty-three.

quantum · Decay

Named alongside it

The objects these essays reach for when they reach for this one.

ScreeningBohr radiusEnergy levelsPeriodic tableProbability densityQuantisationWavefunctionZero-point energyAccidental degeneracyBeta decayBinding energyCentrifugal barrier

All concepts