Illustrated Physics
physics, drawn
Concept

Energy levels — where it appears

The discrete energies a bound system is allowed, arising from a counting condition on a wave that has to fit its own boundaries. Their differences are what a spectrum shows, so a set of emitted wavelengths is a subtraction table rather than a list of properties.

Named by 12 essays across 3 fields — each of them below, with the objects they name alongside it.

Hydrogen's emission lines, where they are actually seen. Every transition down to level 1, 2, 3 in hydrogen, drawn at the wavelength it emits, on a logarithmic axis in nanometres. The Lyman series begins at 121.5 nm and crowds toward its limit at 91.1 nm; The Balmer series begins at 656.1 nm and crowds toward its limit at 364.5 nm; The Paschen series begins at 1874.6 nm and crowds toward its limit at 820.1 nm. Only the Balmer series has lines in the visible band, which is why it was the one found first.

The spectrum is a subtraction, not a list of values

An atom emits a handful of sharp wavelengths and nothing in between. They are not the atom's energies — they are the differences between them, which is why the lines come in families that crowd onto a limit.

quantum · Atomic spectra 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 One well, two wells, and the band they become. The energy levels of a chain of identical wells, for 1, 2, 3, 6, 12, 40 of them, with an on-site energy of -4 eV and a coupling of -0.9 eV between neighbours. One well has one level. Two split it into two, 1.80 eV apart. By 40 the levels have filled a band 3.59 eV wide, which is closing on the limit of four times the coupling, 3.60 eV — and no further widening happens however many more wells are added. The count of levels grows with the number of wells; the width of the band does not.

What happens when the wells get close

Two atoms brought together split one level into two. A thousand split it into a thousand, packed into a band whose width stops growing after the third. Whether that band is full or half full is the whole difference between a wire and a window.

quantum · Bands 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 The entropy each degree of freedom has not yet given up. The entropy carried by each kind of degree of freedom, drawn against the temperature at which it orders and hands that entropy over. Lattice vibrations freeze out around room temperature; electron spins in a paramagnetic salt order in the millikelvin range, which is what makes adiabatic demagnetisation work; and nuclear spins hold R ln(2I+1) — 11.5 joules per kelvin per mole for copper — down to some tens of nanokelvin, where their own dipolar interactions finally sort them out. A copper sample at a microkelvin therefore has a large entropy and violates nothing: its nuclear spin system has not reached its ground state, and the third law is a statement about ground states rather than about thermometers.

A law about spectra, not about heat

The third law is usually met as a statement about cooling. Its statistical form is a statement about a spectrum: the entropy of a system in its ground state is k ln g, and it vanishes only when the ground state is unique. Every apparent exception is a degeneracy or a system that never reached its ground state — and copper nuclei carry eleven joules per kelvin per mole down to a hundred nanokelvin without violating anything.

thermodynamics · Third law 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 A swing that dies away and comes back. The envelope of the mean position of a coherent state with 9 quanta on average, in an oscillator whose levels carry a small quadratic term, Eₙ = n + n²/240, over one revival time of 240 oscillator periods. The swing collapses within about 9.1 periods, when the packet has spread round its orbit, and it stays at zero for most of the run. It returns whole at half the revival time, on the opposite side, and whole again at the full revival time; the envelope is summed from the state's energy components and checked against α·exp(−2n̄ sin²χt) to a part in a hundred million. The dashed curve is a classical ensemble started from the same distribution, each member orbiting at the frequency its own energy gives: it collapses in the same way and never returns, its swing at the half and full revival times 0.1% and 0.1% of the start.

The return a classical cloud never makes

Put a swinging quantum packet in a well whose frequency depends a little on the amplitude and it spreads round its orbit until its swing has vanished. That part is not quantum at all: a cloud of classical oscillators does exactly the same. What no classical cloud can do is come back — and the quantum packet reassembles whole, on schedule, splitting into copies on the way, because its energies are discrete.

quantum · Correspondence The levels that refuse to cross. The six energies of sodium 3p against an applied field from zero to 4 crossover fields, 147 T, from diagonalising spin–orbit coupling and the field together. At zero field there are two levels, 515.5 GHz apart. The two states with the largest |mⱼ| are straight lines at every field, because nothing else shares their mⱼ. The other four bend. The two states with mⱼ = −½ approach within 486.0 GHz near 12.3 T and then separate again — √2 ζ exactly, since the coupling between them sets how close they may come — while the mⱼ = −3/2 state falls straight through the lower mⱼ = +½ state at 16.6 T as if it were not there. States that the field cannot mix cross freely; states it can mix exchange character instead, and that exchange is the passage from one pattern to the other.

The field an atom calls strong

A magnetic field splits sodium's two yellow lines into ten, at spacings set by Landé's factors — until the field grows past the one the electron already feels from its own motion, when the ten reorganise into the three a theory without spin predicts. Nothing about the magnet decides which pattern appears. The atom does: the same 45 tesla is a strong field for hydrogen, a middling one for sodium and a weak one for caesium.

quantum · Atomic spectra The floor a state's survival cannot go below. The probability that a quantum state is still found in its initial state, against time measured as its energy spread times time over ħ, for four states with the same spread. The shaded region under cos²(ΔE t/ħ) is forbidden by Mandelstam and Tamm's theorem, and every curve — each a sum of phases over the state's energies — stays out of it. Two equally weighted levels run along its edge and reach an orthogonal state at exactly π/2, the fastest any state with this spread can. The same two levels driven off resonance, with the same spread, never get further than a survival of 0.500. Three equally spaced levels become orthogonal only at 1.7101, 1.0887 times the limit, and a coherent state never does, bottoming out at 0.0183. A spread of energy is permission to change, not an obligation.

The fastest a state can stop being itself

Time has no operator, so the energy–time relation cannot be the commutator inequality it resembles. What stands in its place is sharper: a state whose energy is spread by ΔE cannot become a different, orthogonal state in less than πħ/2ΔE, and cannot do it faster than its mean energy above the ground state allows either. Two equally weighted levels reach both limits exactly. Nothing else does.

quantum · Uncertainty 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 A current that falls every 4.9 volts. The share of electrons reaching the anode of a mercury-vapour tube against the accelerating voltage, from a simulation of 3000 electrons at each voltage: the electrons must arrive at the grid with more than 1.5 eV to climb the last small retarding voltage, and lose 4.886 eV — the energy of mercury's first excited state — whenever they hit an atom with at least that much, after a random further distance averaging 0.03 of the gap. The current rises with voltage, then collapses each time the electrons have gained just enough to excite an atom and too little left to reach the anode: minima at 6.3, 11.2, 16.1, 21.0, 25.8 V, about 4.9 V apart. Energy was being handed to the atoms in lumps of 4.886 eV and in no other amount — the first direct evidence, in 1914, that an atom's internal energy is quantised.

The electrons that pay in fixed amounts

Fire electrons through mercury vapour and raise the voltage that drives them, and the current they carry should simply rise. In 1914 James Franck and Gustav Hertz found it rising, then collapsing, then rising again, over and over, every 4.9 volts. Below that energy an electron bounces off a mercury atom and keeps almost everything; above it, it can hand the atom exactly 4.9 electronvolts and no other amount. The atom will accept energy only in the size of the gap between its levels — shown here by collisions rather than by light, and misread by its discoverers as something else entirely.

quantum · Atomic structure

Named alongside it

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

QuantisationSelection rulesAtomic spectraAtomic structureDegeneracyFine structure constantScreeningSpinAbsorptionAngular momentumBohr radiusExclusion principle

All concepts