Spectrophotometry — where it appears
Named by 23 essays across 6 fields — each of them below, with the objects they name alongside it.
What the instrument reports
A spectrophotometer sees a sample through a slit of finite width, at a finite number of wavelengths. What it writes down is the truth convolved with its own bandpass, and nothing in the file says which values were measured and which were invented.
Most things are pale in the infrared
A spectrophotometer stops at 780 nanometres and a black cotton shirt reflecting five per cent of visible light reflects more than half the near infrared. The measurement everybody has and the quantity a camera integrates are different quantities, and nothing in the first says so.
Five nanometres is a choice
Every integral here is taken in five-nanometre steps, and the interval has never had to be defended. Coarsening it to twenty costs daylight two hundredths of a colour difference and a fluorescent tube six and a half — and which way of coarsening is used decides a further factor of six.
A tolerance needs a second number
Two samples one colour difference apart can be read almost identically by everybody or two units apart by the worst-off twentieth, and which of those it is depends on how far apart their spectra are — a quantity every spectrophotometer has already measured and none of them prints. Adding it as a second field predicts the population three times better, and at the tolerances where it matters it is right about a third of the decisions the difference alone gets wrong.
Measured with an aperture, seen with an eye
A spectrophotometer averages a halftone patch and reports one reflectance. An eye blurs it first and compresses afterwards, and the average of a concave function is below the function of the average — so a resolvable screen looks darker than it measures, by fourteen lightness units at a coarse ruling and by nothing at a fine one. The correction a press applies is the same size and has no viewing distance in it.
An instrument has a geometry
Every reflectance here arrives through a model with a bandpass, a sampling interval and no position at all. Real instruments say where they were standing, and the two standard answers disagree by ΔE00 8.35 on a dark gloss sample — a difference that adds rather than multiplies, and that no adaptation removes.
A surface that is not a multiplication
Every argument here about what light does to a surface begins by multiplying two spectra together. A surface with a brightener in it takes light at one wavelength and returns it at another, so it is a full operator rather than a diagonal one — and it does not have a reflectance at all.
A reflectance is a diagonal
A reflecting surface returns light at the wavelength it arrived at, so its whole description is one number per wavelength. A fluorescent one returns it somewhere else, so its description is a square matrix — and the curve every instrument reports is that matrix's diagonal with the rest of it folded in at whatever weight the lamp happened to give.
An instrument brings its own light
ISO 13655 names four measurement conditions and they are usually read as four degrees of care. They are not. They are four different quantities — on an unbrightened sheet all four agree to a rounding, and on a brightened one they are up to seven and a half units apart, with every instrument in calibration and every answer correct.
Three numbers cannot see a line
An instrument that returns three filtered readings of a spectrum determines a three-dimensional projection of it and is exactly blind to the other seventy-eight. On daylight that costs almost nothing; on a fluorescent tube, three quarters of the lamp lies in the part no reading reaches, and adding filters recovers it slowly.
The colour is right first
A reconstruction of a lamp from twelve filtered readings gets its colour right to half a unit while two thirds of its spectrum is still unmeasured. That combination is not a partial success — it is the exact condition under which a spectral prediction made from the reconstruction will be confidently wrong.
An aperture is a filter
A measuring aperture throws away the light that came back outside it, and the light that comes back furthest is the light at the wavelengths the sample absorbs least. So an aperture does not attenuate a translucent sample evenly — it attenuates its peaks more than its troughs, which is a filter whose transmission curve the sample itself decides.
Either disc can be the wide one
Every standard on translucent samples says to illuminate a larger area than is measured, and explains it by saying that light leaks out of the lit spot. That is true and it is not the reason, because the instruction works equally well the other way round — measuring a larger area than is lit gives a reading just as exact. The error is a product of two apertures and either one being wide kills it.
Which index to buy an instrument for
Four departures from the colour integral, ranked by what they cost and by what it would take to remove each one. The ranking by cost and the ranking by price are almost exactly reversed — the two largest are removed by specifying a lamp and by widening a table, and the two that need new hardware are the two smallest.
The slit is what makes it legal
Point-sampling a mercury line at five nanometres costs a colour difference of one unit, and a laser projector thirty-seven. Integrating the same spectrum through the five-nanometre slit every spectrometer already has costs 0.014 and 0.19. The blur anybody would remove if they could is what makes a coarse table honest.
The instrument is one observer exactly
A spectrophotometer has no observer uncertainty. It computes through the 1931 tables to the last bit, reproducibly, forever — which is its whole value and is also why it cannot report the three colour differences of observer spread between itself and whoever is looking at the sample.
Two slits are not one slit
A spectrometer's slit is what makes a coarse table honest, for a lamp and for a notched sample alike. But a colour is a sum over the product of the two, and a notch measured through one slit and a lamp measured through another are not the product measured through a slit. Under a smooth light the difference is nothing. Under a fluorescent tube a notch on the mercury line comes out 0.73 colour differences off from two slits — worse than no slit at all for some notches — and 0.02 off from one slit on the reflected light.
A linear repair for a bilinear loss
The Stearns correction sharpens a table blurred by a triangular slit, and the obvious question was whether applying it to a lamp's table and a sample's restores the product the two of them are wrong about. It restores four fifths of the damage and cannot touch the rest: a three-term filter is linear, the covariance two separately blurred tables discard is bilinear in the two factors, and no linear operator applied to each factor separately produces a bilinear term. What is left is ten times the one-slit answer, at every position of the notch.
One slit, two requirements
A line lamp wants a wide slit, because a wide slit spreads a line where a coarse grid can see it. A notched sample wants a narrow one, because a wide slit fills the notch the grid could have resolved. An instrument has one slit. Measured on the two requirements separately the best widths are five nanometres and one; measured on the two together the best is three, which is neither — and it costs twelve times what the lamp alone would cost and thirty-four times what the sample alone would.
A finer table is a worse table
A real interference filter is not a Gaussian notch. It is an etalon, with pass bands a nanometre or two wide spaced twenty-three apart, and a five-nanometre grid steps over them. Resampled from the maker's one-nanometre table its colour is out by five colour differences under every fill-in rule — the three rules agree to three decimals, because none of them is ever handed a sample inside a feature. The same filter measured through a five-nanometre slit is out by 0.03.
A second slit buys a quarter
A line lamp wants a five-nanometre slit and a notched sample a one-nanometre slit, so an instrument with a slit for each should do much better than one with a single compromise. Over sixty-eight notches under a fluorescent tube, it does better by 28 per cent. One slit on the reflected light does fifteen times better than the best pair, and an oracle choosing the best pair for every notch is still six times worse. The error was never that the factors were flattened; it was that they were flattened separately.
The tables cannot bound what they discarded
A colour computed from a lamp's blurred table and a sample's blurred table is wrong by the covariance the two blurs threw away, and Cauchy–Schwarz bounds a covariance by two variances. With the true variances the bound always holds and sits fifteen times above the error. With variances read from the tables it fails on six of sixty-eight notches under a fluorescent tube and twenty-two under a laser projector — on the line, where the error is largest. A blurred table does not carry the width of a line, and the covariance depends on it.
A declared width buys a factor of two
A colour engine given two separately blurred spectral tables cannot bound its own error from them, and the bound that always holds — the peak declared and nothing else — sits a median 196 times above the error under a fluorescent tube. Adding one number, the width of the lamp's narrowest feature, brings that to 86. It never fails on any declaration the lamp truly meets, it fails on 47 of 68 notches on one it does not, and its rank correlation with the error it bounds is 0.27.
Named alongside it
The objects these essays reach for when they reach for this one.
BandpassMeasurement conditionSpectral structureWavelength gridInstrumentMeasurement errorSpecificationIntegrationQuality controlFluorescentMeasurement uncertaintyReflectance