Concept

Screening — where it appears

The reduction of a charge's field by the other charges that gather around it, so that a distant probe sees much less than a near one. In an atom it removes the accidental degeneracy of the hydrogen levels: an orbital that penetrates the core sees nearly the full nuclear charge for a small fraction of its time, and 0.88 per cent is enough to move 3s half a hartree below 3d.

Named by 17 essays across 7 fields — each of them below, with the objects they name alongside it.

One level, split by the speed of the electron in it. Hydrogen's n = 2 level on the left at the scale of the whole spectrum, and the same level on the right at a scale ten thousand times finer. The gross structure puts it 3.4014 electronvolts below the ionisation limit; the relativistic and spin–orbit corrections then split it into a lower pair, j = ½, and an upper, j = 3/2, separated by 45.3 microelectronvolts. That gap is 1.331e-5 of the level's own binding energy, which is exactly α²/4 — so the size of the splitting is a measurement of how fast the electron is going, α being its speed in units of c on the innermost orbit. The same physics in sodium is larger by four orders of magnitude: its two D lines at 588.995 and 589.5924 nanometres differ by 2.133 millielectronvolts, which is 1.01e-3 of the transition energy, because the outer electron of sodium penetrates to where the nuclear charge is far from screened and the correction goes as the fourth power of the charge it sees.

The line that is really two

Sodium's yellow line is two lines six-tenths of a nanometre apart, and the gap is not a property of the light. It is a splitting of the atom's own level, caused by the electron's magnetic moment sitting in the field it sees because it is moving — and its size, relative to the level it splits, is exactly α²/4.

quantum · Atomic spectra

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 $The charge a plasma hides. The potential around a charge in a plasma, as a fraction of the bare Coulomb potential at the same distance, against distance measured in screening lengths. The electrons crowd toward the charge and the ions move away until the rearrangement cancels the field, and what is left falls as exp(−r/λ_D) on top of the ordinary 1/r. At one screening length the potential is already down to 37 per cent of the bare value, at three to 5 per cent, and at ten to 4 × 10⁻⁵ — so a charge in a plasma is invisible beyond a few λ_D, and the long range of the Coulomb force, which is what makes electrostatics awkward everywhere else, is simply gone. The screening length at 10¹¹ m⁻³ is 3.8 mm at 300 K, 6.9 mm at 1000 K, 21.8 mm at 10000 K, rising as the square root of the temperature because a hotter electron is harder to hold in place. Drawn this way the three curves coincide exactly: the shape is universal and the only thing a plasma's density and temperature decide is the length written on the axis.$

The long-range force that does not reach

The Coulomb force falls off as slowly as gravity does, which is what makes electrostatics awkward — every charge is in principle in contact with every other. Put the same charge into a plasma and it becomes invisible beyond a few millimetres, because the mobile charges around it rearrange until its field is cancelled. What is left is a screened potential with a definite range, and that range is what makes a plasma a plasma.

astrophysics · Plasma oscillation

How much a wrap holds, against how many turns it is. The ratio of the two tensions a rope can hold across, against the number of turns it is wrapped, for coefficients of 0.1, 0.25, 0.5. The axis is logarithmic because the law is exponential, so each line is straight and its slope is the coefficient. At µ = 0.1 one turn multiplies by 1.9, two turns by 4 and three by 7 — so a person pulling with the strength of one arm holds a load that a small crane would be needed to lift. The practical consequence is the one a sailor states as a rule: turns are cheap and each is worth as much as the one before it, which is a statement about a constant factor rather than a constant force.

The part of the wrap that is actually gripping

The capstan equation gives the largest tension ratio a wrap can hold, and almost nothing spends its life at that limit. Below it the wrap divides in two: an idle arc doing nothing at all and an active arc creeping and carrying the whole exponential — and the division explains a belt's speed loss and its squeal.

mechanics · Friction

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 pressure a charged gel develops. The swelling pressure against the gel's fixed charge density, for several salt concentrations, on logarithmic axes. Each curve has two straight parts with different slopes, and both limits are checked against the solution rather than read off the plot. Where the fixed charge is small compared with the salt the pressure goes as the square of the charge divided by four times the salt: the bath's ions screen the fixed ones, and doubling the salt halves the pressure. Where the fixed charge dominates, every counterion it demands is an extra particle in the gel and the pressure goes as the charge itself. At 15 mM salt, a gel with 200 mM of fixed charge develops 427 kPa; At 50 mM salt, a gel with 200 mM of fixed charge develops 306 kPa; At 150 mM salt, a gel with 200 mM of fixed charge develops 150 kPa; At 500 mM salt, a gel with 200 mM of fixed charge develops 49 kPa. Cartilage carries a fixed charge of a couple of hundred millimolar from the sulphated sugars on its proteoglycans, sits in a bath of about 150 mM, and develops a swelling pressure of an atmosphere and a half — which is what holds a joint apart and carries the load across it.

The swelling a membrane cannot stop

Give the thing a membrane holds back an electric charge and the small ions that can cross are no longer free to distribute themselves. Two conditions — neutrality on each side, and equal chemical potential for the salt — fix where every ion goes, and they leave the charged side with more particles than the other. That excess is what holds a joint apart, and it is why a cell has to spend a third of its energy pumping.

fluids · Osmosis $The colours a draining film runs through, and the end of them. The fraction of light a free soap film reflects, against its thickness, at three wavelengths — 450, 550, 620 nm — computed from the sum over multiple reflections rather than from the two-beam approximation. The three curves peak at different thicknesses, which is why a draining film runs through a sequence of colours as it thins. Below about 11 nm every curve is under a tenth of a per cent and the film looks black. At zero thickness the reflectance is exactly zero, checked before the figure is drawn: the two surfaces reflect equally and half a cycle out of step, so a film much thinner than a wavelength cancels itself. That is the whole of why a black film is black. Nothing is absorbing; the film is there and has simply stopped being able to interfere constructively at any visible wavelength — which means the blackness is a measurement, and a film that has gone black is known to be thinner than about a tenth of a wavelength without anything being measured directly.$

The film that goes black before it bursts

A soap film drains, runs through every interference colour, and then stops reflecting anything at all. The black patch is not a hole and not a film about to break: it is the thinnest and most stable state the arrangement has, held apart by a pressure between its two surfaces that only exists at distances of nanometres.

fluids · Surface tension

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

An absorption that goes up when the photon gets harder. Mass attenuation coefficients for 4 materials against photon energy, both logarithmic, from tabulated measurements interpolated between. Away from a threshold every curve falls steeply — a harder photon is less easily absorbed, which is what makes X-rays penetrating. At a K edge the curve jumps upward: the photon has become able to eject an innermost electron, a whole new population becomes available, and the absorption multiplies by 4.4 for iodine at 33.17 keV and 4.0 for lead at 88 keV. That is a discontinuity in a material property as a function of frequency, and nothing in the classical description of absorption produces one. It exists because absorption at these energies is a transition of a bound electron rather than a loss in a medium.

The steps in an absorption curve

Every absorption law up to this point is smooth — a fixed loss per cycle, a relaxation, a power of frequency. Take the photon energy up to where it can eject an electron from an atom and the curve acquires steps, and they go the wrong way: the material becomes suddenly more opaque to a harder photon. Iodine absorbs four times as strongly at 33.4 keV as at 33.0, and that discontinuity is why it is injected into people.

waves · Attenuation $Most of a chain's counterions never leave it. The fraction of a charged rod's counterions lying within a distance r of it, against r in rod radii on a logarithmic axis, for a charge parameter ξ = 4.2 — the Bjerrum length of water, 0.7135 nm, over a charge spacing of 0.17 nm, which is DNA's. Each curve is the Poisson–Boltzmann solution for the rod at the centre of a cell of radius 10², 10⁴, 10⁶ rod radii, with its counterions checked to neutralise it exactly. Diluting the solution widens the cell by four decades at a time, and a counterion free to go anywhere in the cell ought to spread with it; instead each curve keeps a plateau near the rod whose height does not change. At the inflection of every curve the enclosed fraction is 0.762, which is Manning's 1 − 1/ξ, and the plateau sits there: 76 per cent of the counterions stay bound to the chain however dilute the solution, and only 24 per cent spread through it.$

The counterions that never leave the chain

Dilute a solution of DNA a million times and its counterions ought to scatter through the whole volume. Three quarters of them do not. A line of charges closer together than the Bjerrum length — 0.71 nm in water — holds on to its counterions however much room they are given, until the chain's charge is cut back to one per Bjerrum length, and every osmotic pressure, swelling gel and packed virus built from such chains is set by that length rather than by the chemistry.

fluids · Osmosis $The innermost electron of an atom with Z = 79, with and without relativity. The probability of finding the innermost electron at each distance from a nucleus of charge 79 (Au), with the distance in units of a₀/Z so that the non-relativistic curve is the same for every element. The dashed curve is Schrödinger's, r² e^(−2Zr/a₀). The solid curve is Dirac's exact ground state, r^(2γ) e^(−2Zr/a₀) with γ = √(1 − (Zα)²) = 0.817. It is pulled in towards the nucleus: its mean radius is 0.878 of Schrödinger's, a contraction of 12 per cent, and it has a sharper peak close in. Nothing about the nucleus has changed; the electron, moving at an appreciable fraction of the speed of light near it, simply behaves as a heavier particle, and a heavier particle is bound more tightly and more closely.$

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 $Hydrogen ionised by heat at one end and by crowding at the other. The ionised fraction of hydrogen against the density of nuclei, at 5,000 K, 10,000 K, 20,000 K, from Saha's equation with the binding energy lowered by the neighbouring charges (solid) and without the lowering (dashed). Thin gas is ionised by the room a free electron gains; compression takes the room away and the gas recombines, as the dashed curves continue to do for ever. The solid curves turn round: at 5,000 K the gas is least ionised, 2.5·10⁻⁴ per cent, near 10²⁶ per cubic metre; at 10,000 K the gas is least ionised, 0.41 per cent, near 10²⁷ per cubic metre; at 20,000 K the gas is least ionised, 12 per cent, near 10²⁸ per cubic metre, and by 6·10²⁸ per cubic metre — 0.10 g/cm³ — every curve is fully ionised, because the ground state no longer exists. That density does not depend on the temperature at all.$

The pressure that ionises

Squeeze a hot gas of hydrogen and Saha's equation says it recombines: a free electron has less room to be in, and room was what paid for its freedom. Squeeze it far enough and it comes apart again, completely, at any temperature — not because the room has grown but because the atom has nowhere left to be. Crowded to within a few atomic radii of each other, hydrogen atoms have no bound state, and their electrons, freed by pressure alone, form a metal. Deep inside Jupiter most of the planet's hydrogen is in that state.

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

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 $Two ways to be wrong, and the apparatus that sees each. The fractional sag of the potential at the centre of a charged spherical shell below the shell's own, on a logarithmic axis, against the shell's radius in metres, also logarithmic, for two different departures from Coulomb's law. If the force fell as 1/r^(2+ε) with ε = 10⁻¹⁶, the sag is 3.07·10⁻¹⁷ whatever the shell's size (dashed): the law has no length in it, so neither does its failure. If the photon had a mass of 10⁻¹⁴ eV, the sag is (μR)²/6 (solid): 4.3·10⁻²⁰ for a centimetre shell and 4.3·10⁻¹⁶ for a metre. A mass introduces a length, and the signal grows as the square of the apparatus compared with it — so the strongest bounds on a photon mass come from the largest fields, not the most sensitive laboratories.$

The mass that would make Gauss's law leak

Gauss's law says the flux out of any closed surface counts the charge inside, whatever the surface's size. If the photon had even a tiny mass, that would stop being true: the field of a charge would die off exponentially beyond a length ħ/mc, the flux through a large sphere would fall short of the charge, and the inside of a charged shell would no longer be field-free. There are two different ways Coulomb's law could fail, and they are caught by opposite strategies. A wrong exponent has no length in it and shows equally in any apparatus; a mass has a length, and shows as the square of the apparatus's size. That is why the tightest limit on the photon's mass comes not from a laboratory but from the magnetic field the solar wind carries past Pluto.

electromagnetism · Gauss's law

Like menisci attract, unlike menisci repel. Cross-sections of a water surface with two small floating bodies, drawn with menisci of the shape K₀(r/ℓc) that a small floater makes, exaggerated vertically. Left: two light bodies, each pulling the surface up round itself as buoyancy pushes it up against the surface; each sits on the other's slope and is drawn towards it, as a bubble rises — the two climb together. Right: a light body that raises the surface beside a heavy one that depresses it; each sits on the other's slope the wrong way and they drift apart. The deformations reach a few capillary lengths, 2.71 mm for water, and the rule is the whole of the Cheerios effect: cereal clumps, and cereal gathers at the wall of a bowl the milk wets.

The cereal that gathers at the edge of the bowl

The last few pieces of cereal in a bowl of milk clump together and drift to the side of the bowl. Nothing is pulling on them but the milk's surface. Each floating piece bends the surface round itself, and a second piece sitting on that bend has somewhere to slide: like menisci attract, unlike menisci repel, and the reach of the force is a few capillary lengths, 2.7 millimetres for water. The arithmetic is the arithmetic of charged lines in two dimensions, screened by gravity, and it says why leaves gather on a pond, why bubbles on coffee drift to the cup's rim, and why particles smaller than about ten micrometres do not clump this way at all.

fluids · Capillarity

The square root of an X-ray's energy, one step per element. The square root of the energy of each element's Kα X-ray line, in units of the Rydberg energy, against its atomic number, for 24 elements from aluminium to lead (dots), with Moseley's law, √(3/4)·(Z − 1), drawn as a line. The points march up in equal steps, one per element, because each step adds one proton to the nucleus and one unit to the charge the falling electron feels. When Moseley first did this, in 1913–14, the line had gaps where no known element fell: the numbers marked, 43, 61, 72 and 75, were found later as technetium, promethium, hafnium and rhenium. At high atomic number the points rise above the line, by 6 per cent for lead, because the innermost electrons there move fast enough for relativity to deepen their binding.

The X-ray line that counts the protons

Strike a metal with fast electrons and it gives off X-rays at a few sharp energies characteristic of the metal. In 1913 Henry Moseley measured the strongest of them for element after element and found that the square root of its energy rose in equal steps, one step per element — as if something inside each atom were being counted. It was the charge on the nucleus. The periodic table had been ordered by weight; Moseley's line ordered it by protons, fixed the elements it was missing, and showed that an electron deep inside a heavy atom behaves like the electron in hydrogen, with the charge turned up.

quantum · Atomic spectra

The dust a plasma freezes into a crystal

Sprinkle microscopic plastic spheres into a glowing discharge and each one charges itself to tens of thousands of electrons, because the plasma's light, fast electrons reach it far more often than its heavy ions. The charge holds the grains up against gravity in the sheath above the electrode, and it makes their mutual repulsion so strong compared with their jiggling that, at room temperature, they freeze into a hexagonal crystal with a lattice spacing a camera can resolve. A plasma, the hottest and most disordered state of matter, is where the most strongly ordered one was found to form most easily.

astrophysics · Plasma oscillation

Named alongside it

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

Atomic structure Energy levels Equilibrium Periodic table Absorption Binding energy Bohr radius Chemical potential Coulomb force Debye length Effective nuclear charge Electrostatics

All concepts