Illustrated Physics
physics, drawn
Concept

Debye model — where it appears

A solid's heat capacity computed by counting its sound waves as modes of a box and cutting the count off at the shortest wavelength the lattice allows. It gives the T³ law at low temperature and the classical value at high, and its only material input is one temperature fixed by the speed of sound.

Named by 5 essays across 3 fields — each of them below, with the objects they name alongside it.

Entropy that is still there at absolute zero, counted and measured. Four substances whose entropy does not go to zero when they are cooled as far as anybody can cool them, with the entropy counted from the arrangements they froze into beside the entropy measured by integrating their heat capacities. Ice is the famous one: every oxygen has four hydrogen bonds and the rule is that two hydrogens sit near it and two far, which leaves six of the sixteen placements legal, and Pauling's count of the whole crystal collapses to R ln(3/2) = 3.371 J per mole per kelvin against a measured 3.41 — an agreement to one per cent from an argument on one line. Carbon monoxide and nitrous oxide are the easy cases, molecules that can lie either way round in the lattice and have too little to gain by choosing. The worst of the four is off by 25 per cent, which is the honest state of this subject: the counts are crude, they ignore the correlations between neighbouring choices, and they still land within sight of a calorimeter. What the figure is really about is that the third law has an escape clause and the escape clause is measurable. A perfect crystal has one arrangement and zero entropy; a crystal that ran out of time while it had many has the logarithm of however many it stopped at, permanently.

The entropy that is still there at zero

The third law says a perfect crystal has no entropy at absolute zero. Ice has 3.41 joules per kelvin per mole left over, and the number can be recovered from one line of counting — two hydrogens near each oxygen and two far, six legal arrangements out of sixteen, R ln(3/2). The law has an escape clause and the escape clause is measurable.

thermodynamics · Third law How many modes a square has below a given wavenumber. The number of vibration modes of a square with wavenumber below k, counted exactly — every eigenvalue of this region is a closed form, so the staircase is the true count and not an estimate. There are 265 of them below k = 60. The smooth curves are what Weyl's law predicts. The upper one is the leading term alone, the area times k² over 4π, and it is too high by 21.5 modes at the right-hand edge; the lower one subtracts the perimeter term, the perimeter times k over 4π, and is out by 2.4. The content of the law is that the count depends on the region through its area and its perimeter and — to this order — through nothing else at all: not through its shape, not through where its corners are, not through whether it is convex. The staircase's steps are the individual modes, and they cluster where two different pairs of indices give the same wavenumber. That the count is smooth in the large while being a staircase in the small is what makes a mode count usable in thermodynamics, where it appears as a density of states and never as a list.

How many ways there are to vibrate

A drum has infinitely many modes, and below any given frequency it has a finite number of them. That number turns out to depend on the drum's area and the length of its rim and — to the accuracy anybody uses — on nothing else about its shape. Almost every result in thermal physics that involves waves is an application of that count.

waves · Standing waves How much slower a warm atom ticks. The fraction by which a free atom's clock runs slow on average because of its thermal motion, (3/2)kT/mc², against temperature on logarithmic axes, for five atoms used in clocks or tests of relativity: hydrogen 4.1 × 10⁻¹¹ at 300 K, aluminium ion 1.5 × 10⁻¹² at 300 K, strontium 4.8 × 10⁻¹³ at 300 K, caesium 3.1 × 10⁻¹³ at 300 K, mercury ion 2.1 × 10⁻¹³ at 300 K. Every line falls in proportion to the temperature and to one over the mass. A clock aiming at one part in 10¹⁸ must hold strontium below 0.63 mK and hydrogen below 7.3 µK — or know their temperature well enough to correct for it. Pound and Rebka's gravitational shift across 22.5 m, 2.46 × 10⁻¹⁵, is marked for scale.

The clock that runs slow because it is warm

Every atom in a gas is moving, and every moving clock runs slow. The first-order Doppler shifts of a hot gas cancel on average; the time dilation does not, because it has only one sign. A hydrogen maser at 40 °C runs slow by four parts in a hundred billion from this alone, a nucleus in a crystal runs slow even at absolute zero, and the first test of gravitational time dilation nearly drowned in a one-kelvin temperature difference.

relativity · Time dilation How well a diamond-like crystal conducts heat, from 1 K to 1000 K. The thermal conductivity of a model crystal with diamond's sound speed and Debye temperature, from kinetic theory applied to its phonons, against temperature on logarithmic axes: natural carbon in a sample 1 mm across, isotopically enriched carbon, and natural carbon in a sample 0.1 mm across; copper's room-temperature 400 W/m K is marked for comparison. The model is calibrated to natural diamond's 2,200 W/m K at room temperature. At low temperature the conductivity rises as the cube of the temperature, limited by the sample's walls; at high temperature it falls as umklapp collisions shorten the phonons' paths. Between, it peaks: 3.7·10⁴ W/m K at 100 K for the natural crystal; 7.8·10⁴ W/m K at 94 K for the enriched crystal; 1.2·10⁴ W/m K at 126 K for the thin natural crystal. The model gets the shape — the rise as the cube of the temperature, a peak near 100 K, the fall — but overestimates the heights, because it leaves out the phonon collisions that conserve momentum and every defect but isotopes; measured enriched diamond peaks near 4 × 10⁴ W/m K. An insulator with no free electrons still conducts heat five times better than copper at room temperature.

The gas of sound that carries a diamond's heat

Diamond has no free electrons and conducts heat five times better than copper. What carries the heat is a gas — not of molecules but of quantised sound waves, phonons — and the kinetic theory that gives the conductivity of air gives the conductivity of a crystal with the same formula: a third of heat capacity times speed times mean free path. The gas is strange in two ways. At low temperature its particles cross the whole crystal without meeting anything, so the conductivity depends on how big the sample is. And at room temperature one atom in a hundred being a neutron heavier is enough to scatter its fastest-oscillating members.

thermodynamics · Kinetic theory A heat capacity that goes up and comes down. The heat capacity per system, in units of Boltzmann's constant, against temperature in units of the level spacing over k: for a system with two levels (red), Schottky's hump x²eˣ/(1 + eˣ)², x = Δ/kT, and for a harmonic oscillator with the same spacing (blue), which climbs to one k and stays there. Both are frozen out when kT is well below the gap. The oscillator then fills its unending stack of levels and reaches equipartition's value. The two-level system peaks at 0.439k when kT = 0.417Δ, and then, with both levels nearly equally occupied and nothing higher to go to, it stops absorbing heat: its capacity falls back towards zero as 1/T².

The heat capacity that goes up and comes down

Equipartition promises every way a system can move a fixed share of heat, and for a harmonic oscillator the promise is kept: once the temperature is high enough, it holds one k per oscillator and goes on holding it. A system with only two levels cannot keep it. It absorbs heat while its upper level is filling, then stops — the two levels equally full and nowhere higher to go — so its heat capacity rises to a peak and falls back to zero. The hump, named after Walter Schottky, is the signature of a degree of freedom with a ceiling, and the area under it counts how many states were there.

thermodynamics · Equipartition

Named alongside it

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

Heat capacityEntropyAbsolute entropyAtomic clockBlackbodyThe Boltzmann factorBoundary conditionDensity of statesEigenvalueEquipartitionErgodicityIsotope effect

All concepts