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 9 essays across 3 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

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, not of the nucleus alone.

The half-life that chemistry can change

A nucleus has no clock, the usual account goes, and 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 $The innermost electron of an atom with Z = 79, with and without relativity. The probability of finding the innermost electron at each distance from a nucleus of charge 79 (Au), with the distance in units of a₀/Z so that the non-relativistic curve is the same for every element. The dashed curve is Schrödinger's, r² e^(−2Zr/a₀). The solid curve is Dirac's exact ground state, r^(2γ) e^(−2Zr/a₀) with γ = √(1 − (Zα)²) = 0.817. It is pulled in towards the nucleus: its mean radius is 0.878 of Schrödinger's, a contraction of 12 per cent, and it has a sharper peak close in. Nothing about the nucleus has changed; the electron, moving at an appreciable fraction of the speed of light near it, simply behaves as a heavier particle, and a heavier particle is bound more tightly and more closely.$

The metal that is yellow because it is heavy

Gold sits directly below silver in the periodic table, with the same arrangement of outer electrons, and by every non-relativistic calculation it should look like silver. It is yellow because its innermost electrons move at more than half the speed of light. The mass that motion adds pulls the s orbitals in, the tightened s level drops towards the d band beneath it, and the gap an absorbed photon must bridge shrinks from the ultraviolet into the blue. The same contraction is why mercury is a liquid.

quantum · Atomic structure

The contraction the forces work out for themselves

Relativity usually introduces length contraction as a consequence of how moving observers disagree about simultaneity, not as something that happens to matter. There is a second way to reach the same number, and it is worth knowing because it is the way the idea was first found. Take an atom, accelerate its nucleus gently, and compute what the electron does using only Maxwell's field of a moving charge and the law of motion. Nobody tells the orbit to contract, and it does, by exactly 1/γ, while each turn takes exactly γ times as long. The forces holding matter together work out the contraction for themselves.

relativity · Length contraction $What correlation is worth, to a helium atom and to H⁻. The energy needed to remove the second electron, by three descriptions, as a fraction of the measured value, for the negative hydrogen ion and for helium. Helium: one shared orbital 23.07 eV, one electron in and one out 23.83 eV, measured 24.59 eV — the simple picture is 94 per cent right. H⁻: −0.74, 0.362 and 0.755 eV — the simple picture is not merely inaccurate but has the wrong sign. The energy the simple picture misses — the electrons avoiding each other — is about 1.5 eV in both; in helium it is a small correction to 24.6 eV, and in H⁻ it is everything.$

The ion that exists because its electrons keep apart

Add a second electron to a hydrogen atom and it holds on, by three-quarters of an electronvolt. The simplest respectable calculation says it should not — that the two electrons, sharing one orbital, repel each other more than the proton can hold them, and the ion falls apart. The same calculation gets helium's energy right to two per cent. The difference is not a failure of the method but a measure of what it leaves out: the two electrons avoiding each other. In helium that is a small correction. In the negative hydrogen ion it is the whole of the binding, and that ion is what makes the Sun opaque.

quantum · Atomic structure

Named alongside it

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

Screening Bohr radius Energy levels Periodic table Effective nuclear charge The Lorentz factor Probability density Quantisation Wavefunction Zero-point energy Absorption Accidental degeneracy

All concepts