Crystallography & Symmetry
patterns derived from their groups
The collection

Every essay — page 11

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

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.

monoclinic: 9 twin laws, 1 of them exact. The twin laws of a monoclinic lattice: a two-fold about the row [uvw] paired with the plane (hkl) it is meant to be a mirror in, kept when the twin index is at most six and the obliquity at most six degrees, which are Friedel's own limits and are a convention rather than a theorem. 9 of the 9 are listed. The index n is how many lattice nodes there are per node the operation restores, computed from the integers and checked against the sublattice built from the plane and the row. The obliquity is the angle between the row and the plane's normal: 1 of these laws have none, and for those the operation restores a sublattice exactly.

The index and the angle a twin misses by

Whether a crystal will twin on a given operation is decided by its lattice, not by its structure. Two numbers decide it: how many lattice nodes there are per node the operation restores, and how far the operation is from being a symmetry at all. Both are computed from integers, and one of them is a fiction that has to be labelled as one.

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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: how many independent invariants there are at each degree. The number of independent polynomial invariants of the plane point group 4mm, one bar per degree from 0 to 8. The heights are the coefficients of the Molien series, computed from an integer recursion on the trace and determinant of each operation. A dot above a bar marks a degree where the same number has been computed a second way, by averaging every monomial of that degree over the group and taking the rank of the result — a computation sharing no code with the first. The two agree at every degree checked. Degrees where the bar is absent hold no invariant at all: for 4mm that is every odd degree below the first invariant, and it is a statement about which functions the group refuses to leave alone.

How many invariants of each degree

A group moves the plane about, and some polynomials do not notice. How many independent ones there are at each degree is a sequence of integers, computed here by a recursion on traces and again by averaging every monomial — two routes that share no code and agree everywhere.

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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.

p6m: freezing Γ2 leaves p31m. The same crystal three times. On the left, a pattern with the full symmetry of p6m. In the middle, the displacement each atom takes under the order parameter — the arrows are the mode, drawn in the first colour for one set of atoms and the second for the other where there are two. On the right, the atoms moved by a small multiple of those displacements. The group of the right-hand pattern is p31m, of index 2 in the parent, and it was found by the detector from the point set alone. The prediction — which operations carry the displacement field to itself — is made separately, from the mode and not from the points, and the two lists of operations are identical.

An order parameter is a representation

The quantity that measures a lost symmetry is not a number the physics chooses freely: the parent group mixes its components, so it carries a representation, and the symmetry that survives is what leaves its value alone. Every prediction here is checked by moving the atoms and asking the detector.

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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.

Unreflected copies stop at 1 ring. Copies of the hat, all of the same handedness, covering a core of 1 ring of hexagons — 9 tiles, every cell covered once. At 2 rings the same search runs to exhaustion and returns nothing: there is no such covering, and the failure is a proof for that region rather than a search that gave up. The reflected copy is not a convenience of the drawing; the tiling cannot proceed without it.

The tile that needs no reflection

One shape tiles the plane and never repeats, and it does it with copies of both hands. Cut the tiles out of card and that is nothing; ask for it in a molecule, where handedness cannot be undone by turning something over, and it is the whole question.

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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.

656 sets, every one decided. Every set of one, two, three and four tiles over two colours — sixteen tiles exist in all, so these are complete lists rather than samples — reduced by relabelling the two colour alphabets, and each set decided by the two half-searches. The last column is the one that matters: it is empty. At these sizes there is no room for a set that tiles the plane and admits no periodic tiling, which is the residue undecidability lives in. The smallest aperiodic set is known to have eleven tiles and four colours.

How much room a hard question needs

No algorithm decides whether a set of tiles covers the plane. Every set of four or fewer tiles over two colours is nevertheless decided here, exhaustively, in under a second — because the sets that defeat the two half-searches have nowhere small to live.

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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.

[001]: 8 of 24 faces. The 24 faces of the form {210} of a cubic crystal, stereographically projected, with one zone marked. The great circle is the set of directions perpendicular to the axis [001]; the 8 faces on it are the zone, and each is on it because the integer sum hu + kv + lw is exactly zero. No length and no angle enters that test. Faces of the lower hemisphere are drawn faintly.

A zone is a vanishing dot product

Look at a crystal and the obvious thing about it is that the faces run in bands — sets whose edges are all parallel. A face belongs to such a band exactly when three integers multiplied by three others sum to zero. No length enters, no angle enters, and that is why every index on a nineteenth-century mineral specimen is still the index used now.

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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.

One crystal, two rows: one streaks and one does not. Two rows of reflections from the same faulted crystal, at a fault rate of 0.05, each drawn against the same row from a perfect one. The upper row has h − k not divisible by three, so each layer contributes a different cube root of unity and the sequence of layers enters the sum: the sharp peaks collapse into a streak. The lower row has h − k divisible by three, the phase factor is one, every layer scatters in step, and the peaks are exactly as sharp as in the perfect crystal. The sorting is an integer condition — a reflection either can see the stacking or cannot, decided by h − k modulo three — which is the most direct evidence there is that the disorder is in the stacking and not in the layers. The profiles are averaged over 16 independently faulted crystals, because one crystal gives speckle rather than a diffuse profile.

The streaks a faulted stack makes

Close packing settles two directions and leaves the third to chance. A crystal that chooses wrongly now and then has a lattice in the plane of its layers and none across them — and its diffraction pattern says so, with some rows of spots as sharp as ever and others smeared into streaks, sorted by an integer condition.

10 figures What each Laue class buys, in measurements per reflection. The eleven Laue classes, with how many distinct reflections a block of indices holds under each and how many times a data set measures the average one. The redundancy is always below the order of the class and the gap is the special reflections. This is the number an experiment is planned around: repeated measurements of what symmetry says must agree are the only estimate of precision that does not come from a model, so a triclinic crystal has to be turned through far more of the sphere than a cubic one to be measured as well.

Every reflection, several times over

A diffraction experiment does not measure each reflection once. Symmetry relates a reflection to the others of its orbit, and those are the same reflection seen from another direction — so a hundred thousand measurements may contain twelve thousand reflections, each observed eight times.

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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.

Six of the ten plane classes have a free invariant ring, and four do not. Every plane point group, with the degrees of the generators of its invariant ring, whether the ring is free, and the relation where it is not. The six generated by their own reflections — 1, m, 2mm, 4mm, 3m and 6mm — have two generators whose degrees multiply to the order of the group, which is Chevalley's theorem checked rather than quoted. The four without reflections — 2, 4, 3 and 6 — need three generators in two variables, so one polynomial relation ties them together, and the degree that relation appears at is printed at the right of its row. Nothing here is a lookup: the generators are found degree by degree as the invariants the earlier ones do not reach, and the relation is the kernel of the map back to polynomials.

The groups whose invariants are free

Six of the ten plane classes have an invariant ring generated by two polynomials with no relation between them, and the six are exactly those generated by their own reflections. The degrees of those generators multiply to the order of the group, and their excess counts the reflections.

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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.

4mm: which phase depends on where the order parameter points. The plane of a two-dimensional order parameter, with each sampled direction marked by the symmetry that survives when the parameter points that way. The directions along which some operation is preserved are drawn large with a spoke to the centre; the general directions, where nothing survives, are the small faint marks between them. One representation, several phases — and the symmetry does not say which of them a crystal takes. That is decided by terms in an energy, which no symmetry argument supplies: what symmetry supplies is the list a material must choose from.

Which way the order parameter points

A two-component order parameter has a direction as well as a size, and the symmetry that survives depends on where it points. One representation therefore offers several low-symmetry phases — and symmetry, having produced the list, has nothing to say about which one a crystal takes.

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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.

342 unlabelled spots, cell volume 52. A bag of 342 reflection positions with no indices on them, collected out to a bound of 3 on each index. Their pairwise differences generate the reciprocal lattice; a basis of that is taken by integer elimination and then reduced, and the reduced basis is printed. Its determinant is 52, which is the volume of the cell the reflections were computed from — so the cell has been recovered from positions alone, with no intensity used anywhere.

A cell from a bag of spots

A single-crystal experiment returns a list of directions with no labels on them. Recovering the cell is recovering the lattice those directions generate, and the whole of it is take differences, reduce, read the answer. What no quantity of data settles is whether the lattice found is the true one or a sublattice of it.

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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.

A peak that grows, and not fast enough. The strongest peak of three chains, divided by the square of the number of letters, as each chain is lengthened. A Bragg reflection is a sum of terms in phase, so its intensity grows as the square of the count and this number settles: the Fibonacci chain and the period-doubling chain both do, at exponents of about two. The Thue–Morse chain does neither — its strongest peak grows, so it is not diffuse scattering, and it grows more slowly than the square, so it is not a Bragg peak. The fitted exponents are printed beside each curve and no threshold enters the comparison.

Neither a peak nor a bump

A chain whose strongest reflection grows as the length to the power one and a half. A Bragg peak grows as the square and a diffuse bump grows as the length itself, so this is neither — and the essay that ruled out the first possibility could only say so by quoting a theorem.

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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.

4: three generators in two variables, and the one relation between them. The invariant ring of 4 needs 3 generators, of degrees 2, 4, 4, and three functions of two variables cannot be algebraically independent. The relation between them is found rather than quoted: every monomial in the generators of the degree at which they can first be dependent is written out, the map back to polynomials in x and y is formed, and its kernel is the relation. It is then evaluated at points of the lattice, where all three generators take integer values and the combination comes to exactly zero. A group with a reflection has no such relation, which is the same statement as its ring being free.

Three invariants and one relation

Four of the ten plane classes need three invariants where two variables can only support two, so exactly one polynomial identity ties them together. The identity is not recognised or recalled: it is the kernel of a linear map, computed and then checked at lattice points where every term is an integer.

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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 often each block of 5 occurs. Every block of length 5 in the fibonacci chain, with its frequency from the Perron eigenvector of the block substitution and again from a count over a chain of 46368 letters. The two share nothing: one is a linear algebra problem over a matrix of integers, the other a loop over a string. The eigenvalue of the block matrix is the inflation factor of the letter matrix, which is a second check and a stronger one — a chain inflates at one rate whatever length of window is being counted.

How often each patch occurs

That a patch has a frequency at all is the ergodic theorem. What the frequency is turns out to be an eigenvector: the substitution acts on blocks as well as on letters, the block matrix has a Perron vector, and its entries are the frequencies exactly. For the Fibonacci chain those entries take three values at every length, and the three values are the three gaps of a rotation.

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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.

the honeycomb net, unfolded over 3×3 cells. The infinite graph the quotient graph names, drawn over 3 by 3 cells with the home cell outlined. Each edge of the quotient becomes one edge per cell, running to the cell its voltage names; the drawing adds coordinates the net does not have, and they are the placement in which every vertex sits at the average of its neighbours. two vertices, three edges, degree three — the graph of graphene and of every hexagonal mesh.

A structure with the distances thrown away

Keep which atoms are joined and throw away where they are, and what is left is an infinite graph that can be written on a postcard: a few vertices, a few edges, and a pair of integers on each. Two things about that writing-down are free, and neither of them changes the net.

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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 twin fraction, recovered from a moment and nothing else (12 atoms). A structure of 12 atoms twinned at each of 6 fractions, with the second moment of its intensity distribution measured and the fraction solved back out of it. The recovery is within a few hundredths as far as thirty per cent — 4 rows here — and 4 of the 6 fractions get a number at all. Beyond thirty per cent the relation flattens: the derivative of 2α(1−α) vanishes at a half, the two roots meet, and a small error in the moment becomes a large one in the fraction. Where the sampled moment falls below 1.5 the quadratic has no real root and the estimate refuses rather than clamping, which is why a nearly perfect twin is the hard case in practice rather than the easy one.

A twin hides in the statistics

A twinned crystal scatters as two orientations at once and the detector cannot separate them. What arrives is a sum of two intensities — and adding two independent quantities narrows a distribution, which is a signature no model of the structure is needed to read.

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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.

p4m: freezing Γ3 leaves pmg. The same crystal three times. On the left, a pattern with the full symmetry of p4m. In the middle, the displacement each atom takes under the order parameter — the arrows are the mode, drawn in the first colour for one set of atoms and the second for the other where there are two. On the right, the atoms moved by a small multiple of those displacements. The group of the right-hand pattern is pmg, of index 4 in the parent, and it was found by the detector from the point set alone. The prediction — which operations carry the displacement field to itself — is made separately, from the mode and not from the points, and the two lists of operations are identical.

The cell a zone-boundary mode doubles

An order parameter that alternates from cell to cell keeps only half the translations, so the frozen structure has a cell twice as large and reflections that were never there before. The phases at such a wavevector are ±1, so the whole computation stays in exact integers.

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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 diffuse intensity of an alloy with α₁ = -0.46. The diffuse part of the scattering across the wavevectors an 12 × 12 block can be asked about, one square per wavevector with darkness the intensity. The marked squares are where the average structure scatters — the sharp part, which is what a Bragg reflection is. The diffuse maximum here is at (0.50, 0.50), which is the zone boundary: the alloy is trying to alternate, and a crystal that succeeded would put a sharp reflection exactly there. Summed over every wavevector, the intensity is exactly one per site whatever the correlations are — order moves scattering about, it does not create it.

The average scatters sharply and the rest does not

A crystal whose lattice is perfect and whose occupation is not scatters in two parts: the average structure gives Bragg reflections, and the variance is spread over everything between them. The split is exact, the total is one unit per site whatever the disorder does, and an ensemble of n arrangements mislays exactly a fraction 1/n of it.

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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.

the kagome net: 4, 8, 14, 18 at the first four shells. The vertices of the kagome net at graph distance one, two, three and four from a chosen vertex, each marked with its distance. Distance here is a number of edges and nothing else — no length enters, and the shells are drawn on the barycentric placement only so that they can be seen. The counts are 4, 8, 14, 18, 22, 28, 30, 38, 38, 48, 46, 58, which is the net's coordination sequence.

Counting outwards

How many vertices lie one step from a vertex, two steps, three? The counts settle into a straight line — but for some nets only along the even distances, with a different line along the odd ones, alternating for ever. The period is measured, and it is not always one.

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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.

A triangle sliding from one mirror to another. Two vertices fixed and the third slid along a line. At the left end the triangle is isoceles about the vertical, at the right end it is isoceles about a different line, and both ends have a mirror — so the measure is exactly zero at both, by cancellation rather than by a search running out. Between them the triangle has no mirror at all and the measure rises to 0.0422. The faint curve is the handedness over the same family, which is a different quantity: it has a sign, it is largest where the measure is not, and it does not vanish at either end.

How chiral, as a number

A group answers one bit: a set either has an improper symmetry or it does not. Two shapes can both be chiral and one of them be a mirror-symmetric thing with a substituent out of place while the other is a helix, and nothing in the classification says which is which. A distance does.

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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.

Which order parameters carry a cubic invariant, and therefore cannot grow from zero. Every order parameter of every plane class, with the number of independent cubic invariants it admits. The count is the degree-three coefficient of the Molien series of the representation's image — the same computation the invariant-ring figures make for a different reason — and Landau's condition is that it be zero. Where it is not, a free energy in that order parameter has a term of odd degree, which puts its minimum away from zero the moment the quadratic coefficient does anything at all, so the parameter jumps rather than growing. In the plane exactly two order parameters carry one, and both are the two-dimensional representation of a class with a threefold axis and no sixfold.

The cubic term that forbids a continuous change

A crystal may lose a symmetry gradually only if the quantity measuring the loss admits no cubic invariant. Whether it does is the third coefficient of a Molien series — so a question about how a material changes is answered by counting polynomials.

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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.

How much one site knows about another, by separation. The Warren–Cowley parameters: the average of the product of the occupations of two sites a given vector apart, over every pair in every configuration. The value at the origin is exactly one — a site always agrees with itself — and it falls away with distance, alternating in sign where the alloy prefers unlike neighbours. These numbers are the whole of what the diffuse scattering measures: its intensity at a wavevector is their Fourier transform, computed here separately and agreeing to the last bits of the arithmetic. Nothing about them requires the crystal to be ordered, and their falling away is what short-range order means.

The order a diffuse pattern measures

Where a diffuse maximum sits says what the crystal is trying to become, and its shape is the Fourier transform of how much each site knows about its neighbours. The correlations are a small array of numbers, the intensity is their transform, and neither route to the other loses anything.

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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.

Compatibility at (0, 0) in p4m. Every representation of the little group at (0, 0) in p4m, and what it becomes along two lines out of that point. A one-dimensional representation stays one level and acquires a label; a two-dimensional one splits into two levels of opposite label. The rows where the two columns differ are the point: the same level is even under the mirror that survives along one line and odd under the mirror that survives along the other, so which bands may cross and which must repel is different in the two directions out of one point. Labels are the characters on the classes, computed rather than named.

Which levels join which, on the way out of a point

A degeneracy at a symmetry point is forced by the little group there. Move off the point and the little group shrinks, the degeneracy is free to split, and which pieces it splits into is decided by restricting a character. That restriction is what joins a table of isolated points into a band structure.

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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.

How many components a property may have, at each rank and in each class. One row per plane point group, one column per rank of a fully symmetric property tensor, with the number of independent components in each cell — counted by averaging the tensor over the group index by index, and equal at every entry to the Molien coefficient of that degree. A symmetric property of rank r is a form of degree r, so Neumann's principle and the invariant ring are the same arithmetic in two notations. The last column is the elastic tensor, which is not fully symmetric — symmetric within each pair of indices and under exchanging the pairs — and its counts are not in the table to its left. A property with its own symmetries needs its own average, and that is why the elastic constants are not read off a degree.

The parts a property splits into

A symmetric property of rank r is a polynomial of degree r wearing indices, so the number of components a class permits it is a coefficient of an invariant ring's series. The elastic tensor is not a polynomial in disguise, and its counts are not in that table — which is the most useful thing about it.

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