Crystallography & Symmetry
patterns derived from their groups
The collection

Every essay — page 10

One idea per essay, ordered so that the earlier ones set up the later ones — but nothing here depends on being read in sequence.

Order without repetition

Penrose tilings and quasicrystals — patterns with long-range order, five-fold symmetry, and no repeating cell at all.

9 approximants, period 2 to 89. The approximants of the Fibonacci chain: the n-th Fibonacci word taken as a unit cell and repeated. Each is a perfectly ordinary periodic crystal — it has a lattice, a cell and a space group — and each has the composition of the quasicrystal to the accuracy a ratio of Fibonacci numbers can manage, since its long and short tiles are consecutive Fibonacci numbers and their ratio is a convergent of the golden ratio. The last column is where the approximant stops agreeing with the infinite chain letter for letter: always past its own period, because the infinite word begins with every finite Fibonacci word, and never for ever. At order 9 the error in the composition is -3.87e-4, and it falls by a factor of τ² at every step up the sequence.

The crystal you get by rounding τ off

Everything aperiodic about a Fibonacci chain comes from one irrational number in the slope of a cut. Replace it by a fraction and the whole construction survives: the same lattice, the same strip, the same rule, and a chain that is periodic — agreeing with the quasicrystal for a length that grows with the denominator.

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Symmetry at work

Crystal forms, twins, domain walls and grain boundaries. Mineralogy, metallurgy and ferroelectrics each worked these out separately, and every one of them turns out to be an orbit or a coset of a group already built here.

Four ways to lay a second row on the first. The same shape four times, with the upper row related to the lower one by a translation, a half turn, a glide and a mirror. In each case the upper row is pushed down until it touches, and the number is the density that results. The three that keep the shape the same way round come out within two per cent of one another; the mirror packs at 78 per cent of the best of them — 22 per cent less dense — because it presents a protrusion to a protrusion. Stated the other way round, the best of the four is 28 per cent denser than the mirror; the two percentages are the same measurement against two different bases, and neither is the other.

The four plane groups a molecule packs in

A molecule is not a disc: it has bumps and hollows, and packing it tightly means getting one molecule's bump into another's hollow. A mirror puts a bump against a bump. Filter the seventeen by that one observation and four survive — and the space groups the structural literature is mostly made of are the three-dimensional version of the same four.

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Lattices

The repeating scaffold underneath every crystal. Five in the plane, fourteen in space, and no others — a classification with a short proof.

Every plane lattice, shaded by Σ|v|^(−4). The region every plane lattice is one point of, with each point shaded by the sum of the inverse powers of the lengths of that lattice's own vectors, at equal cell area — dark where the sum is small. The square lattice is the ringed point on the vertical axis and the hexagonal one is at the corners, which are the same lattice on two bases. The minimum is at the corner, and it is at the corner at every exponent tried. That is not the same statement as the densest packing, which is decided by the shortest vector alone: this sum counts every shell, and there was no reason in advance for the two questions to have the same answer.

The lattice that minimises a sum

Packing discs asks about the shortest vector alone. Summing an inverse power over every vector of a lattice asks about all of them at once, and there was no reason in advance for the two questions to have the same answer. They do — at every exponent, and the measurement says by how much and where it cannot say.

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How it is known

A crystal's structure is read from the pattern it scatters. The reciprocal lattice, systematic absences, and what an experiment can and cannot see.

pmg: 80 of 80 restricted. The reflections of pmg inside a window of ±4, with the ones whose phase symmetry restricts to two values picked out. Every solid spot has a structure factor that must be real up to a fixed rotation — a sign, in effect — whatever the atoms turn out to be, and the pale ones have a phase symmetry says nothing about. The 4 palest spots carry two incompatible restrictions at once, which leaves them nothing to be but zero. Which spots these are was computed from the operations, before any structure existed.

The zones that behave as if there were a centre

The phase problem is usually stated as though symmetry had nothing to say about phases. It is true of most reflections and false of some, and which is decidable from the group alone: where an operation carries a reflection onto its own negative, the phase is confined to two values half a turn apart, computed from that operation's translation.

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What symmetry decides

Thirty-two classes, enumerated rather than listed — and then the one thing they are for outside crystallography's own bookkeeping: which components of a physical property a crystal is permitted to have before anybody measures it.

6mm: 6 irreducible characters on 6 classes. The character table of the plane point group 6mm, constructed rather than quoted. The columns are its 6 conjugacy classes, with the number of operations in each; the rows are its 6 irreducible representations, of dimensions 1, 1, 1, 1, 2, 2. The dimensions satisfy 1² + 1² + 1² + 1² + 2² + 2² = 12, which is the order of the group, and that identity together with the count of classes is what proves the list complete. Every entry is an exact element of the twelfth cyclotomic ring; the decimals shown are the numerical value of an integer vector, not a computed approximation.

What a group does to a function

A symmetry operation moves points about, and two hundred essays here have watched it do so. It also acts on everything defined over those points — a density, a displacement, a wave — and that action is linear, which turns a group of motions into a set of matrices and every question about it into arithmetic.

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Order without repetition

Penrose tilings and quasicrystals — patterns with long-range order, five-fold symmetry, and no repeating cell at all.

The allowed energies of the Fibonacci chain, level by level. The set of energies at which a wave neither grows nor decays, for periodic approximants of the Fibonacci chain of 5, 8, 13, 21, 34 and 55 sites. Each row has exactly one band per site, and each band splits into smaller ones at the next level rather than growing. Nothing in the picture converges to an interval: the gaps opened at one level survive at every level after it, and the limit is a Cantor set — closed, containing no interval at all, and of measure zero, which is a theorem of Sütő's rather than something these six rows prove.

A spectrum that is a Cantor set

A wave in a periodic chain has bands with gaps between them. A wave in the Fibonacci chain has gaps inside the gaps, at every scale — and the traces that decide where they are obey a recursion with a quantity it cannot change.

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Lattices

The repeating scaffold underneath every crystal. Five in the plane, fourteen in space, and no others — a classification with a short proof.

A gap of exactly 1.00. The two folded bands with the ordering switched on. The faint curves are the same bands before it, crossing at the boundary of the reduced zone; the ordering couples them there and separates them by exactly twice its own strength. The gap appears at the wavevector where the superlattice's extra reflections appear, and for the same reason: both are the Fourier component of the potential at that wavevector.

A bigger cell, a smaller zone

Ordering two kinds of atom onto a sublattice adds reflections to the diffraction pattern and opens a gap in the levels. It is one fact told twice: the same Fourier component of the potential, at the same wavevector, doing the same thing.

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What symmetry decides

Thirty-two classes, enumerated rather than listed — and then the one thing they are for outside crystallography's own bookkeeping: which components of a physical property a crystal is permitted to have before anybody measures it.

The ten plane classes, and the dimensions they permit. Every crystallographic point group of the plane, with one block per irreducible representation and each block as wide as its dimension. Nine of the ten have only one-dimensional representations; 4mm, 3m and 6mm carry a two-dimensional one, drawn in the measured colour. Nothing is wider than two, and the sum of the squares of the widths in each row is the order of that group — the identity that says the row is complete.

How large a degeneracy may be

Symmetry can force two things to have the same value, and in a crystal it can force three. It can never force five, and the reason is a sum of squares — the same kind of arithmetic that forbids a five-fold axis, arriving at a question about levels rather than about rotations.

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Symmetry at work

Crystal forms, twins, domain walls and grain boundaries. Mineralogy, metallurgy and ferroelectrics each worked these out separately, and every one of them turns out to be an orbit or a coset of a group already built here.

A circuit that closes on the wrong point: (1, 0). A square lattice with one extra half-column, drawn as a graph: the rows above the core have one more site than the rows below, and the core is the site at the end of the extra column. The path is 4 steps east, 4 north, 4 west and 4 south — the same number out as back — and it ends one lattice vector from where it started. Every one of the 12 circuits in the survey that goes round the core fails by that vector, and all 10 that miss it close exactly.

The circuit that does not close

A defect in a crystal is usually introduced as a picture — an extra half-row of atoms, a wedge taken out. What makes a defect a crystallographic object rather than a drawing is a closure failure: walk a closed circuit through the lattice and come back to the wrong point, by an amount the lattice itself decides.

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The classification

Exactly seventeen ways to fill the plane with a repeating pattern. Not a fact to memorise: a theorem, with a finite argument and no eighteenth case.

3 whole-number solutions: (6, 3), (4, 4), (3, 6). Every pair of whole numbers from three to 12, with the mean face size across and the mean degree down. A square in the first colour is a pair satisfying one over p plus one over q equals a half exactly — the flat case, where a periodic net is possible — and there are 3 of them: 6 and 3, 4 and 4, 3 and 6. The lighter squares above and to the left have a sum greater than a half, which is a closed polyhedron rather than a plane tiling; the ones below and to the right have a sum less than a half and belong to a surface of negative curvature. The plane is the boundary between them and it is thin.

Three answers in whole numbers

One over the face size plus one over the degree equals a half. Ask for whole numbers and there are exactly three answers, which are the three nets everybody has drawn since childhood — and the pairs on either side of them are a closed polyhedron and a plane the plane has no room for.

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How it is known

A crystal's structure is read from the pattern it scatters. The reciprocal lattice, systematic absences, and what an experiment can and cannot see.

⟨cos Φ⟩ against κ, 379 triplets. The mean cosine of the triplet, binned by the concentration κ = 2|E₁E₂E₃|/√N, for the 379 triplets of a structure of 24 atoms whose reflections all exceed |E| = 1.2. The curve is Cochran's I₁(κ)/I₀(κ), computed from the distribution and not fitted to anything; the points are measured, with the number of triplets in each bin printed above. They agree to 0.1 root-mean-square. The measured points sit slightly above the curve throughout, which is the finite structure showing: Cochran's derivation assumes atoms placed at random and there are only 24 of them.

Three phases that do not move when the origin does

A phase is a property of the description, not of the crystal: shift the origin and every one of them changes. A sum of three phases whose indices add to zero does not change, because the shifts cancel. That sum is the smallest thing about a structure that a diffraction experiment could in principle know, and it is not distributed at random.

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Into space

Seventeen becomes two hundred and thirty. Screw axes, glide planes, and the translations that no choice of origin can remove — the operations a flat surface has no room for.

p3m1 at (0, 0): the levels the little group requires, and the ones measured. The levels of the p3m1 model at (0, 0), with degenerate ones drawn thick. The little group there has order 6, and its characters predict levels of dimensions 1, 1, 2, 2. The measurement is 1, 2, 2, 1, and the account is "unitary". The values are numerical and the multiplicities are read at a stated gap; the prediction they are compared against is exact.

Where two levels must meet

At most wavevectors nothing of a crystal's symmetry survives, and its levels are as unconstrained as any operator's. At a handful of them a whole point group survives, and where that group has a two-dimensional representation, two levels are obliged to coincide — before anything about the material is known.

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Lattices

The repeating scaffold underneath every crystal. Five in the plane, fourteen in space, and no others — a classification with a short proof.

Sublattices of index n, in space. How many sublattices a three-dimensional lattice has at each index, beside the plane's answer, with the Hermite enumeration and the coefficient of ζ(s)ζ(s−1)ζ(s−2) in separate columns. The two are computed by routines sharing no code, and a row where they disagreed would be a failure rather than a result. The last column counts the ones that survive every operation of the cubic group, and it is almost always empty.

The three that stay cubic

A lattice in space has far more sublattices than one in the plane — 651 of index sixteen against 31 — and almost none of them keeps the symmetry it came from. The ones that do exist at indices m³, twice m³ and four times m³, there is exactly one at each, and they are the primitive, face-centred and body-centred cubic lattices, arrived at by asking which sublattices keep a symmetry rather than by enumerating centrings.

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What symmetry decides

Thirty-two classes, enumerated rather than listed — and then the one thing they are for outside crystallography's own bookkeeping: which components of a physical property a crystal is permitted to have before anybody measures it.

4mm: a degeneracy tuned into existence, and gone at the next weight. Four invariant operators on one orbit of 8 points under 4mm, differing only in the weight given to a single class of pairs. The first column is not a choice: it is the value that weight has to take for two levels of different symmetry to arrive at the same number, found by sweeping the weight and closing on the crossing, and the two levels there agree to 1.0e-9. The character table predicts levels of sizes 1, 1, 1, 1, 2, 2; the tuned column shows 1, 1, 1, 2, 3 and every other column shows the predicted pattern again. That is the whole of what an accidental degeneracy is — a property of one choice of weights, not of the group — and it is why the weights have to be moved before a degeneracy is called forced. A degeneracy the group requires would be in all four columns, because nothing respecting the symmetry can lift it.

A coincidence the group did not ask for

Two levels sitting at the same value look identical whether symmetry required it or not. The difference is testable: move the numbers the symmetry does not decide and watch what survives, because a degeneracy the group forces cannot be shifted by anything the group leaves alone.

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Into space

Seventeen becomes two hundred and thirty. Screw axes, glide planes, and the translations that no choice of origin can remove — the operations a flat surface has no room for.

pgg at (1/2, 0): the operators multiply up to a sign. Every product of two Bloch operators of the little group of (1/2, 0) in pgg, against the operator of the product. They agree up to a scalar, and the scalar is +1 or −1: 4 of the 16 products come back with a minus sign. No rephasing removes them, and the search that says so tries every assignment of twelfth roots of unity to the operators. A representation that multiplies only up to this sign cannot be one-dimensional, because scalars commute and these operators do not. Each entry is an exponent modulo twelve, so the table is exact.

A glide sticks two levels together

The translation attached to a glide moves no wavevector at all. It comes back as a phase factor, and at the edge of the zone the factor is minus one — after which the operators of the little group no longer multiply the way the group does, and no rephasing repairs it.

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The classification

Exactly seventeen ways to fill the plane with a repeating pattern. Not a fact to memorise: a theorem, with a finite argument and no eighteenth case.

A wavevector of thirds, and the boxes that cannot see it. Which sizes of box can carry the wavevector at the corner of a hexagonal zone. The characters of the box's translation group are its wavevectors, and there are exactly N² of them — the fractions with denominator dividing N. A wavevector of thirds is therefore present in a box of three, six, nine or twelve cells and absent from one of two, four or five: not approximated badly, not resolved coarsely, absent. A mechanism or a level living there is invisible to such a calculation, and that is the practical content of a mechanism count depending on the cell it was looked for in.

Crystallography in a box

A calculation over a crystal is not performed on a crystal. It is performed on a finite block with its edges glued, and the block has a symmetry group of its own — finite, complete in one direction and missing something decisive in the other.

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Symmetry at work

Crystal forms, twins, domain walls and grain boundaries. Mineralogy, metallurgy and ferroelectrics each worked these out separately, and every one of them turns out to be an orbit or a coset of a group already built here.

square: 3 dislocations, 2 stable. The short lattice vectors of the square lattice, grouped into orbits under its own automorphism group of 8 operations. Two vectors of one orbit are the same defect seen from different directions, so the number of kinds of dislocation is the number of orbits — 3 out to 4 times the shortest squared length. Each orbit has its own colour. Solid arrows are stable: no pair of shorter lattice vectors adds to them with a smaller total of |b|². Dashed ones split, and 1 of the orbits do. Which splits is decided by comparing integers; that the energy goes as |b|² at all is Frank's rule and comes from elasticity, not from here.

How many dislocations a lattice has

A circuit round a defect comes back to the wrong lattice point, and the amount by which it misses is a lattice vector. That much is quantised. The next question has a number for an answer: how many *different* dislocations are there? Two Burgers vectors related by an operation of the point group are one defect seen twice, so the answer is a count of orbits.

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Order without repetition

Penrose tilings and quasicrystals — patterns with long-range order, five-fold symmetry, and no repeating cell at all.

How fast a window's answer settles: 1/L on the chain, 1/√L on a shuffle. The largest error a window of each length makes about a block's frequency, over every position the window can take, on logarithmic axes. The upper line is a shuffle of the chain's own letters — same frequencies, no order — and its slope is close to −½, which is the random walk a sequence with no structure produces. The lower line is the Fibonacci chain itself and its slope is close to −1. The frequency of a block in the chain is therefore something a finite window measures rather than approaches: to know it to a part in a thousand needs a window of a thousand tiles, not a million.

The average is the same wherever it is taken

A measurement is made on a window somewhere, and the question is whether the answer belongs to the chain or to the window. For the Fibonacci chain the error falls as one over the window's length; for a shuffle of the same letters it falls as one over the square root, and the two exponents are fitted rather than asserted.

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How it is known

A crystal's structure is read from the pattern it scatters. The reciprocal lattice, systematic absences, and what an experiment can and cannot see.

the most consistent answer has 100 per cent of the signs. 60 runs of the sign procedure from 60 different random starts, each plotted at its self-consistency — a figure computed without any knowledge of the answer — against the fraction of its signs that are in fact right. Throwing out the 1 run that reached the uniform solution — every sign the same, perfectly consistent and physically a single peak — the highest consistency belongs to a run with 100 per cent of the signs right. The ranking works here, and the reason it works is that the cell is small. Nothing in the plot's horizontal axis knows the answer, which is the only reason a procedure of this kind is a procedure at all.

The formula that has the answer already

The tangent formula rebuilds each phase from all the others, and the true phase set is very nearly a fixed point of it — hand it the answer and it hands the answer back. Start it anywhere else and it does not arrive. Having a fixed point and finding it are different problems, and the second is where the subject spent twenty years.

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What symmetry decides

Thirty-two classes, enumerated rather than listed — and then the one thing they are for outside crystallography's own bookkeeping: which components of a physical property a crystal is permitted to have before anybody measures it.

An orbit of 12 points under 6mm, split into 6 kinds. The functions defined on one orbit of 12 points under 6mm form a space of that dimension, and the group acts on it by permuting the points. The character of that action is the cheapest one in the subject — at each operation it is the number of points left where they are — and decomposing it against the table gives the multiplicities on the right. They are whole numbers, they weight the dimensions to 12 again, and the multiplicity of the trivial representation is the number of orbits, which is Burnside's lemma arriving as a special case.

The shell that splits into kinds

The neighbours of an atom carry a space of functions as large as the shell, and the group does not treat that space as one thing. It splits into pieces of a few kinds, in whole numbers, and the count is the cheapest character in the subject: how many neighbours each operation leaves where they are.

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The classification

Exactly seventeen ways to fill the plane with a repeating pattern. Not a fact to memorise: a theorem, with a finite argument and no eighteenth case.

p4m from 3 orbits of waves — detected p4m. A density built as a sum of 3 symmetry-adapted waves of p4m, each of them the average of a plane wave over the group, shaded from light to dark across one cell. The level set of this density — the darkest points of it — was handed to the same detector the pattern figures use, and it reports p4m, which is exactly the group the waves were built from. The waves are invariant by construction, so the density can never have less symmetry than the group; the interesting direction is the other one.

How many waves a group permits

A pattern can be written as a sum of waves instead of as an orbit of a motif, and then the group ties the coefficients together and forbids some outright. Building a density from the permitted ones and handing it back to the detector closes the same loop through a different door — and at low resolution the density has symmetry the crystal has not.

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Order without repetition

Penrose tilings and quasicrystals — patterns with long-range order, five-fold symmetry, and no repeating cell at all.

The hat: eight kites, thirteen sides. The shape a search over the eight-kite polykites returns, drawn on the kite grid it lives in — the Laves tiling [3.4.6.4], in which every hexagon is cut into six kites. The eight kites of the shape are tinted and its outline is drawn heavy. Thirteen sides result, of two lengths only: a half and root three over two, in units of the hexagon's circumradius, with one side of twice the shorter length where two kite edges lie in a line. Its interior angles are 90, 120, 240 and 270 degrees. Nothing about the shape was chosen: it is the one octakite that clears every filter in the search.

One tile, and no period

Every aperiodic pattern in this collection so far needs two shapes. A search over the eight-hundred-and-seventy-three ways of gluing eight kites together, filtered by nothing but whether a shape tiles and whether it repeats, returns exactly one — and it is the shape announced in 2023.

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How it is known

A crystal's structure is read from the pattern it scatters. The reciprocal lattice, systematic absences, and what an experiment can and cannot see.

B = 3.45 against 3.4, K = 0.37 against 0.37. The mean intensity of each resolution shell of a cell of 1194 reflections, divided by Σf² computed from the cell's content alone, and logged. The points fall on a line whose slope gives B = 3.45 against the 3.4 put in, and whose intercept gives a scale of 0.37 against 0.37 — both recovered before a single atom has been placed. The atoms here are independent, so the line is straight at every resolution; the shells below the cutoff are marked in the second colour.

The average that knows the atoms and not where they are

Square a structure factor and average it over a shell of reflections at one resolution. The cross terms — every one of which carries a fact about the arrangement — cancel, and what is left is a sum over the *content* of the cell with no position in it anywhere. A scale and a temperature factor come out of that before a single atom has been placed.

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Into space

Seventeen becomes two hundred and thirty. Screw axes, glide planes, and the translations that no choice of origin can remove — the operations a flat surface has no room for.

The honeycomb's two levels meet at K, exactly. The two levels of the honeycomb net along a line from the centre of the zone to its corner. The off-diagonal entry of its two-by-two matrix is the sum of the phases of three bonds, and at the corner those phases are the three cube roots of unity, whose sum is zero — exactly, as an identity in the ring the phases live in rather than as a number that came out small. So the matrix there is the zero matrix and both levels are zero. It is the shortest exact statement of a crossing in this collection.

The crossing at the corner

The honeycomb's two levels meet at the corner of its zone, and the meeting is not approximate. Three phases sum to zero there — an identity between cube roots of unity — so the matrix is the zero matrix, and making the two sites differ opens a gap of exactly that difference.

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