Concept

Spectroscopy — where it appears

The measurement of how matter absorbs, emits or scatters radiation as a function of frequency. Each line sits at an energy difference fixed by the structure that made it, so a spectrum identifies atoms, molecules and nuclei and measures their temperature, motion and surroundings from a distance.

Named by 4 essays across 3 fields — each of them below, with the objects they name alongside it.

A few cycles, and everything about them is two numbers. The strain radiated by a remnant of 62 solar masses spinning at 0.68 of its maximum, as it settles down, with the decaying envelope of its fundamental mode drawn over it. The fundamental rings at 274 hertz and decays in 3.7 milliseconds, which is 1.0 cycles — this is not a bell and it does not sustain. Every frequency and every decay time in the sum is fixed by the mass and the spin alone; nothing about what made the remnant survives into them. What does depend on the collision is how loudly each mode is excited, and the relative amplitudes here are the rough values a merger of two comparable masses produces rather than a prediction.

A few cycles that are only mass and spin

After the orbit is gone there is one object left, distorted, and it settles down by radiating at frequencies that belong to it rather than to the collision. For a black hole those frequencies are fixed by the mass and the spin and by nothing else — so the first mode measured is a measurement and every mode after it is a test, and the test is that four curves in one plane pass through one point.

astrophysics · Gravitational waves
The area under the spacings is the bond. The gap between each vibrational level and the next, against level number, for a Morse well and a Lennard-Jones well with the same depth and the same curvature at the bottom, Λ = 100, in units of the well depth. The sum of the gaps from the lowest level up is the energy needed to break the bond from there. For the Morse well the gaps fall in a straight line to zero, and a straight line through the first 5 of them, extended to zero, encloses 0.9473 against the true 0.9473. For the Lennard-Jones well the gaps start almost the same and fall slightly faster at first — which is what the straight line sees — then trail off in a long tail of small gaps near the top; the same extrapolation from the first 5 encloses 0.7988 against the true 0.9474 — 15.7 per cent short, because the straight line cannot see the crowded levels its data never reached.

The spectrum that weighs a bond

A vibrational spectrum measured near the bottom of a molecule's well gives its curvature, and the curvature says nothing about how deep the well is. Measured further up, it says everything. The levels of a real bond crowd together towards the top, the gap between neighbours falls towards zero, and the sum of all the gaps is the energy it takes to break the bond. A straight line drawn through the gaps that have been measured, and extended to zero, was for decades how bond energies were found — and for a bond with the tail of two neutral atoms it comes out a sixth short.

mechanics · Harmonic approximation
The heights a neutron is allowed to bounce to. A neutron above a horizontal mirror in the Earth's gravity: the potential energy mgz (straight line), the first four allowed energies and, drawn on each, the probability density of the neutron's height. The natural length is z₀ = (ħ²/2m²g)^(1/3) = 5.87 μm and the natural energy mgz₀ = 0.602 peV. The allowed energies are 1.41, 2.46, 3.32, 4.08 peV — pico-electronvolts — and a classical neutron with each energy would rise to 13.7, 24.0, 32.4, 39.8 μm. Each density is an Airy function, with n − 1 nodes, leaking a little above the classical turning height and vanishing at the mirror. The lowest state never touches the mirror and never rises above about 25 μm.

The bounce that comes in fixed heights

A ball dropped on a floor can bounce to any height. A neutron cannot. Slow enough, and resting on a flat mirror in the Earth's gravity, it has a lowest state about fifteen micrometres high, with an energy of 1.41 pico-electronvolts, and a staircase of higher states above it — the first quantum states ever seen in a gravitational field, measured in 2002 with a slit narrower than a hair. Shaking the mirror at 255 hertz drives a neutron from the first state to the second. The staircase is now a laboratory for gravity at distances where nothing else can test it.

quantum · Matter waves
The hyperfine structure, read off a room-temperature cell. The difference between the probe's absorption with the pump off and on, which removes the Doppler hump and leaves only the Doppler-free features, against detuning. The three transitions, labelled by the excited level F′, sit at −423.6, −266.65 and 0 MHz, and the three crossovers midway between them at −345.1, −211.8, −133.3 MHz. In this model, which empties the ground level only by exciting it, the crossover between F′ = 2 and 3 is the second strongest feature and the weak transitions to F′ = 1 and 2 are small. In real rubidium spectra the crossovers are often the strongest of all, because excited atoms can fall to the other ground level and be lost to the transition altogether — optical pumping, which the model leaves out and which deepens every hole the pump burns. The positions do not depend on any of that: the separations between the features are the hyperfine splittings of rubidium's excited state, read to a fraction of a megahertz in a glass cell on a bench.

The lines a warm vapour hides

Shine a tunable laser through a cell of rubidium vapour and the absorption is one smooth hump half a gigahertz wide, though the atoms' own lines are eighty times narrower and three of them lie inside it. The atoms are moving, each sees the light Doppler-shifted by its own speed, and their lines are smeared together. Send a second, stronger beam back the other way and narrow dips appear in the hump at exactly the frequencies of the hidden lines — because only atoms standing still can be talked to by both beams at once. The vapour stays at room temperature and the motion is not removed; it is selected against.

quantum · Atomic spectra

Named alongside it

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

Zero-point energyAiry functionAnharmonicityBlack holeBound stateDampingDegeneracyDissociation energyDoppler broadeningEquivalence principleGravitational wavesHarmonic approximation

All concepts