Crystallography & Symmetry
patterns derived from their groups
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The theme: Symmetry is decidable — page 14

Unusually for a physical science, the central questions here have exact answers computable in integer arithmetic. There is no tolerance to choose and no residual to interpret.
How the space groups are spread over their classes. For each number of groups, how many arithmetic classes carry exactly that many space-group types, in space and in the plane, every count derived from the classes' cohomology and the normaliser's action on it. In the plane ten of the thirteen classes carry one group. In space twelve of the seventy-three carry one, thirty-five carry two and fifteen carry four, so the typical class carries two; the long tail is the orthorhombic and tetragonal classes with eight, ten and sixteen. What a lattice forbids

Two hundred and nineteen over seventy-three

The space groups average three to an arithmetic class, and an average of three could be a few classes carrying dozens or every class carrying a handful. Derived class by class from the cohomology and its normaliser, the answer is the second: twelve classes carry one group, the median carries two, and the largest carries sixteen. Sixty-one of the seventy-three admit a non-symmorphic group, and the step that merges relabellings, which the plane barely uses, removes more than a quarter of the list.

 What refinement takes back from a wrong disorder model. Every directed pair of disorder models sharing an occupancy, 462 in all: data made from one model's averaged structure, the other model refined against them with positions on its own loci, two-component displacement parameters and fixed occupancies. Across is the residual between the two ideal structures; up is the residual after refinement. Points on the dashed line lost nothing to refinement; the median point lost 58 per cent of its residual. Every point on the floor, where the wrong model fits exactly, is one whose loci contain the true model's. What a lattice forbids

What refinement takes back from a wrong model

Two disorder models sharing an occupancy leave averaged structures typically a sixth apart. Refine the wrong one against the right one's data and it takes back more than half of that — all of it wherever its loci contain the true ones. Yet the data still choose, even for a molecule of sixty-four atoms, because a likelihood summed over every reflection sees what no single reflection can, and the wrong model's partial atoms give it away through the size of their displacement parameters, not their shape.

 A row of coefficients for every group. For eight of the seventeen, the number of sublattices of each index that the group's point group carries to itself. A nought means the group has no copy of itself at that index at all. p1 and p2 preserve every sublattice, so their rows are the counts of sublattices themselves — 1, 3, 4, 7, 6, 12 — which is the sum of the divisors. The rows thin out as the point group grows, and p4m and p6m have almost nothing in them. Every row is a sequence a Dirichlet series can be built on, and the next figure is what that series factors into. Into space

A row written as a product

Every group's copies of itself sit at a row of indices, and every row so far has been read one entry at a time. Counting all of them at once turns a row into a Dirichlet series, and every one of the seventeen rows factors into a product over the primes — which is the statement that a copy is a chain of maximal steps, written as arithmetic. The plainest group of all has the most famous series in mathematics.

 Better counting makes an uncorrected smooth error choose the wrong model. Eighteen pairs of disorder models, each decided by the likelihood ratio at the 0.1 per cent level, at sixty-four and a hundred and twenty-eight atoms, as the random error falls from 3% to 1% to 0.3% of the mean amplitude. In each group, the first bar has random error only, the second adds a smooth scale error of 3% across reciprocal space, and the third adds the same error with a degree-two scale surface refined alongside the structure. With random error only, better counting decides more pairs correctly. With the uncorrected smooth error it stops helping and the number decided for the wrong model grows, to three at a hundred and twenty-eight atoms. With the surface refined, the result is the random-only one in every group. What a lattice forbids

Better counting, and the wrong model

A smooth error across reciprocal space, as large as the random one, hardly changes which disorder model the data choose: it enters both models' residuals and cancels from their difference. What it changes is where better data lead. With random error alone, counting harder decides more pairs correctly. With the smooth error left in, counting harder stops helping and starts deciding pairs for the model that did not make the data — at the 0.1% level, and more of them the better the counting.

 Six matrices and eight: a monoclinic normaliser modulo two. For P2/m and C2/m, every 3 × 3 matrix over the field of two elements that preserves the reductions of the two eigen-sublattices of the class's two-fold or mirror — six on the primitive lattice and eight on the centred one — each drawn as a tile of nine squares filled where the entry is one. The whole infinite normaliser reduces into this set, and a dot under each tile marks that some normaliser element with entries −1, 0 and 1 reduces to it. Every tile is realised, and the same holds in all six monoclinic classes. What a lattice forbids

The normaliser only acts modulo two

The space groups were counted as orbits of a small, finite set of changes of basis — only those with entries −1, 0 and 1 — out of normalisers that are infinite in the monoclinic classes. That the counts came out right was evidence, not proof. It becomes proof in two steps. A missing change of basis can only leave the count too high, never too low, so the published totals already force every class. And in the monoclinic classes the infinite normaliser acts on the cohomology only through its reduction modulo two, where the small set already reaches everything.

 Which four-dimensional lattices carry which rotations of order twelve. Six four-dimensional lattices, the order of each one's symmetry group, and how many of its symmetries are of each of the three kinds of order twelve: the single block Φ₁₂, the third-turn with a quarter-turn Φ₃Φ₄, and the quarter-turn with a sixth-turn Φ₄Φ₆. D₄ has 96 of the first among 1,152 symmetries, the two hexagonal planes 24 among 288, and the hexagonal-and-square sum 4 of each of the other two among 96. No lattice has all three, and none has the first with either other. What a lattice forbids

No lattice carries all three twelves

Four-dimensional lattices admit three different operations of order twelve: one that turns a single irreducible block by a twelfth, and two that turn two planes, by a third and a quarter or by a quarter and a sixth. Computing the symmetry group of every kind of four-dimensional lattice that can have a maximal one shows that no lattice carries all three, and none carries the first with either of the others. D₄, the most symmetric of them, has only the first.

 One group without an axis, and as many as the order with one. For a rotation of each order that an integer matrix can have in a small dimension, the number of space groups its arithmetic class admits — computed from the cohomology rather than enumerated. A rotation acting on the smallest lattice that will hold it fixes no direction and admits exactly one group: the symmorphic one, with no screw. Add a direction it leaves alone and the count becomes the order of the rotation, and the extra groups are its screws. The four-fold with an axis gives four, which are P4, P4₁, P4₂ and P4₃; the five-fold with an axis gives five, in five dimensions, where no published table exists to check it against. The classification

The screw a dimension does not have

The extension count is a machine that runs in any dimension, and the seventeen were the case where every step could be checked against a list arrived at four other ways. Run on a cyclic point group it has a closed form two lines long — and it says a five-fold screw axis does not exist in four dimensions, which is a prediction rather than a check.

 One sheet with two faces rolled into two scrolls. The cross-section of a sheet with different atoms on its two faces, rolled three turns into an Archimedean spiral, once with face A outward and once with face B outward. Unlike a tube, a scroll has an inner edge and an outer edge and a radius that grows with every turn, so an isometry of space can neither turn it about its axis nor reverse the direction along the spiral: it can only slide it along the axis, reflect it across the axis, or reflect the spiral itself. What a lattice forbids

A scroll cannot be turned end for end

A sheet with two different faces rolls into two tubes, face A out and face B out, and for forty-six of the eighty layer groups the two tubes are one object whichever way the sheet is rolled. Roll the same sheets into scrolls, spirals with an inner edge and an outer one, and only seventeen keep that. A spiral cannot be turned about its axis or run backwards, so the half-turns and screws that joined the tubes have nothing to act on. What survives is a mirror lying in the sheet, and a two-fold axis lying along the roll.

 Every finite normaliser of a lattice's group, found whole. The fourteen Bravais lattices on primitive bases, with the number of primitive vectors along the axes of their rotations, the order of the lattice's group, and the order of its normaliser in the integer matrices, found by trying every assignment of axis vectors to three independent ones. On the three lattices up to monoclinic the axis vectors lie on one line or none and the normaliser is infinite. On the other eleven it is finite (48, 16, 48, 48, 16, 16, 24, 12, 48, 48, 48), its largest entry is one, and it is exactly the set of matrices with entries −1, 0 and 1 that the space-group census used. What a lattice forbids

A normaliser must permute the axes

The space groups were counted with a small set of changes of basis, and past the monoclinic system nothing had shown that set was the whole normaliser. It is, and the reason is geometric: a change of basis that carries a lattice's group to itself must carry each rotation axis to a rotation axis, so it permutes a finite set of vectors, and past the monoclinic system three of them pin it down. Every such permutation tried, the eleven finite normalisers turn out to be exactly the matrices with entries −1, 0 and 1, and 219 and 230 stand without any table behind them.

 Which sites a smooth error can mislead. For the eighteen pairs of disorder models at three site symmetries, under a smooth scale error of degree two (five molecule sizes) and of degree four (three sizes): how many verdicts of perfect counting go the wrong way, how many pairs no data can decide, the largest correlation between the error and the two models' difference, and how many harmonics of the error's degree the site's group leaves unchanged. At the cubic site the degree-two error correlates with nothing, to rounding, and decides no pair wrongly; the degree-four error, which the cubic site keeps one harmonic of, reaches it. What a lattice forbids

A cubic site is blind to a degree-two error

A smooth scale error left uncorrected made perfect counting choose the wrong disorder model for eight of ninety pairs and sizes, and the obvious way to predict which is to correlate the error with the two models' difference before refining anything. That correlation predicts none of them. What it does predict, exactly, is which pairs can never go wrong: at a cubic site a scale error of degree two correlates with nothing and is absorbed by nothing, because a cubic group keeps no harmonic of degree two. A degree-four error, which it keeps one of, reaches the cubic site at once.

 The first-order prediction against the actual verdict, for every pair and size. The 85 decidable pairs of disorder models at five molecule sizes, each placed by the first-order prediction of the wrong model's misfit minus the right model's, made from the two error-free refinements and their Jacobians, and by the actual difference after refining against data with a 3% smooth error. Shaded quadrants are agreement. 77 agree. Of the 8 wrong verdicts, ringed, 4 are predicted; 4 right verdicts are predicted wrong. What a lattice forbids

The wrong model moves too far for first order

Which disorder models a smooth error will turn the wrong way was left as a calculation to make before any data exist: project the error onto the directions each refinement's parameters can move. Made, it gets the sign of the verdict right in seventy-seven of eighty-five cases, catches four of the eight wrong verdicts and raises four false alarms. Every case it gets wrong is either a near-tie or a refinement that absorbed more than twice, or less than half, of what its first-order directions allow.

 Twelve kinds of operation six dimensions adds, and the lattices that carry them. The twelve rational kinds of operation whose orders first appear in five or six dimensions — 7, 9, 14, 15, 18, 20 (two kinds), 24 (two) and 30 (three) — against six lattices whose symmetry groups were computed element by element. Every kind is carried by at least one. All three kinds of order thirty are carried by A₄ ⊕ A₂, forty-eight symmetries each; the single-block kinds Φ₇ and Φ₁₄ only by A₆, and Φ₉ and Φ₁₈ by E₆ and by three hexagonal planes. What a lattice forbids

The thirties share a lattice

Four dimensions has three kinds of operation of order twelve and no lattice carries all three. Six dimensions has three kinds of order thirty, and one lattice carries every one of them, forty-eight times each. The difference is not the order. One of the twelves is a single block that cannot be split, and no thirty is: thirty needs eight dimensions to be irreducible, so in six it is always a five-fold piece beside a three-fold one, and the lattice that is both pieces holds every combination.

 Three rules for 'square' are three shapes, and the cell falls between them. A measured cell placed by how far it is from each of the two conditions a square cell needs — equal edges across, a right angle up — each in its own standard uncertainties, so the square cells are the origin. Three rules for accepting the cell as square at the five per cent level are three regions. The two-condition χ² accepts inside the larger circle, of radius 2.45; testing each condition separately accepts inside the square of half-side 1.96; reading the distance as if it were one condition accepts inside the smaller circle, of radius 1.96. The measured cell, 2.22 and 0.75 from the two conditions, is inside the first region and outside the other two. Operations

Two conditions are not one condition twice

Whether a plane structure has a higher-symmetry supergroup is decided by its measured cell, and the obvious measure — how many standard uncertainties the cell sits from a right angle, or from equal edges — cannot rank the candidates on its own. A square needs two conditions and a rectangle one, so a single distance means different things on each; counted properly, a square can score above the equal-edged lattices that contain it, and walking up the diagram one condition at a time is the reading that keeps the ranking coherent, at a price that has to be paid in its error rate.

 Three mirrors of a 30–30–120 triangle, closed. A triangle with angles of thirty, thirty and a hundred and twenty degrees, shaded, and every image of it under the group its three side-mirrors generate, within a window. The images alternate between the triangle and its mirror image, and they tile the plane — so the closure is discrete. But the group it produces has a mirror along the triangle's own altitude, drawn dashed, that is none of the three given: the triangle is two copies of the thirty–sixty–ninety triangle, and the group is that triangle's, p6m. The closure found a mirror the generators did not name. Operations

Four groups are made of mirrors

Close the plane from located mirrors instead of rotation centres and the closure is discrete only for four triangles of mirrors — and one of those four manufactures a mirror along its own altitude. Of the ten plane groups that contain a reflection, exactly four are generated by their mirrors; three hold a kaleidoscope at index two, three and four, which are the numbers in front of the star in their orbifold symbols; and three have mirrors in one direction only, which generate nothing along themselves.

 How many reflection operations a plane of each lattice can carry. Every mirror of each of the fourteen Bravais lattices' holohedries, sorted by how many classes of lattice vector lie in it modulo the conventional cell's own translations — which is how many reflection operations any plane of that orientation can carry in any space group on that lattice. Primitive lattices carry one on every plane. Centred ones carry two on the planes their centring vectors lie in: one plane of the C-centred orthorhombic lattice, the diagonal planes of the body-centred tetragonal and cubic ones, and every mirror plane of the face-centred lattices. The rhombohedral lattice, on the hexagonal axes the Tables use, carries three on each of its three mirror planes. None carries four. Into space

Three on a plane, and never four

A reflection plane in a space group carries one operation for each class of lattice vector lying in it, and a face-centred lattice has planes holding two independent centring vectors — enough for four. None of those planes is ever a mirror. The fourteen lattices decide the question without the two hundred and thirty: one, two or three operations on a plane, and never four — with the three on every mirror plane of the rhombohedral lattice, where the Tables' own hexagonal axes put them and the letters have no name for them.

 Every square-lattice superstructure, by the size of its cell. The number of distinct arrangements of two species on the square lattice whose primitive cell holds exactly n sites, for n from one to twelve, logarithmic, counted over every cell shape at once: every sublattice of index n up to the lattice's own symmetry, every colouring of it up to translations and the sublattice's stabiliser, and only those whose true period is that sublattice. Odd prime sizes are low, because only a few cell shapes exist; sizes with many divisors are high. Operations

Every superstructure counted once

The 805 arrangements of two species on a four-by-four cell were never the structures with sixteen atoms: forty-nine of them repeat in a smaller cell, and every sixteen-atom structure whose cell is not a four-by-four square is missing. Counting structures rather than arrangements means counting over every shape of cell at once, and discarding every arrangement that repeats sooner. On the square lattice that gives 2, 2, 4, 11, 16, 40, 48, 148 structures for cells of one to eight atoms, and 22,413 with sixteen.

 Eighty layer groups, over the seventeen plane groups. Each of the seventeen plane groups with a block for every layer group that projects onto it. Every plane group carries one layer whose two faces differ and nothing turns it over, and one with a mirror in its own plane. The rest are turned over by some of their operations, and there is one for each class of two-colouring of the plane group: the pale-dark blocks turn the layer over only with a rotation, a mirror line or a glide line of the pattern, and the dark blocks turn it over on a translation — a glide plane lying in the layer. The totals are 17, 17, 26 and 20, which is eighty. The classification

Eighty is seventeen, seventeen and forty-six

The eighty layer groups are usually quoted, and an earlier count here reached sixty-three and blamed the translations. The eighty follow in three lines from things already counted: a layer group is a plane group with a sign on each operation, and the signs are either all plus, all doubled by a mirror in the layer, or a two-colouring of the plane group — seventeen, seventeen and forty-six. The sixty-three had missed the twenty colourings that turn a layer over on a translation, which are glide planes lying in the layer itself.

 Six groups are made of glides, four of mirrors, eleven of both. For each of the twelve plane groups that contain a reflection, what its mirrors generate on their own, what its glides generate, and what both together generate, counting lattice translations as something the generators must produce. Four groups are generated by their mirrors alone, six by their glides alone — pg, pgg, p4g, p3m1, p31m and p6m — and eleven by the two kinds together; pm is the one they cannot make, because its mirrors are parallel and nothing produces the translation along them. Where a set falls short the cell says how: every coset reached but only part of the lattice, translations in one direction only, or a proper subgroup. Operations

Six groups are made of glides

Four plane groups are generated by their mirrors. Six are generated by their glides, and they are mostly different ones, because a glide done twice is a translation where a mirror done twice is nothing. Closing the plane from located glide lines with their slides reaches six of the seventeen; mirrors and glides together reach eleven, every group with a reflection except pm. The classification does not fall out of the closure, and where it stops says what each kind of reflection can and cannot make.

 Four inversion centres, and a band's charge on each. A square crystal with four atoms in each cell, at the points a quarter of the way along both diagonals, and the four points of the cell that an inversion maps onto themselves: the corner, the midpoints of the two edges, and the centre. None of the atoms sits on one. For each of four versions of the crystal, differing only in which bonds are stronger, the ring marks where the lowest band's charge is centred — computed from the band's Berry phase and predicted from four parities. Each version puts it on a different inversion centre, and in every case on a point with no atom. Into space

Four signs say where the charge sits

In a plane crystal whose only symmetry beyond its lattice is a centre, a band's charge must sit on one of the cell's four inversion centres — and which one is decided by four signs: whether the band is even or odd under inversion at the four wavevectors inversion leaves alone. The centre can be a point no atom occupies, and when the four signs multiply to minus one there is no centre at all, only a charge that winds round the cell.

 I222 and I2₁2₁2₁: the same axes, apart. The two-fold rotation axes of the two space groups on the body-centred class of 222, drawn in one conventional cell seen down its third edge: axes along that edge as diamonds, axes along the first edge as solid lines and along the second as dashed lines, with the height of each written beside it. Both groups have pure two-fold rotation axes in all three directions. In the symmorphic group some axes of different directions cross, at the origin among other places; in the other none does, because the heights of the axes in each direction are a quarter out of step with the positions of the axes in the others. The classification

Two groups no single operation reveals

A space group is non-symmorphic when no choice of origin removes all of its translations at once, and every textbook example has a screw or a glide to show for it. Two of the two hundred and thirty do not need one. Every operation of I2₁2₁2₁, taken on its own, is also a plain rotation about some axis; so is every operation of I2₁3. What makes them non-symmorphic is that their rotation axes never meet — and no diffraction extinction can tell them from I222 and I23.

 Where an antiferromagnet's reflections land. Two cubic antiferromagnets, with their nuclear reflections as dots and their magnetic reflections as triangles, in units of the conventional reciprocal lattice. On the left, a simple cubic lattice with every neighbour opposite: the magnetic reflections sit at half-integer indices, in a layer the nuclear pattern never visits. On the right, a body-centred lattice with the corners up and the centres down: the magnetic reflections sit at integer indices with an odd sum — exactly the reflections the body centring had extinguished, lit up again by the moments. In both, no magnetic reflection falls on a nuclear one. What symmetry decides

Magnetic reflections land where nuclear ones cannot

An antiferromagnet scatters neutrons into places its chemical structure leaves dark, and never into a place it lights. The reason is one line of algebra: the magnetic pattern is the nuclear pattern shifted by half a reciprocal-lattice vector. Each of a lattice's seven halvings is one such shift, and how many of them its symmetry keeps decides how many kinds of domain the magnet must form.

 Every group a symmetric motif can lift a plane group to. The seventeen plane groups arranged by lattice, with an arrow from each group to every group a motif of higher symmetry, placed at some position, turns it into, on the generic lattice of the first. Dashed arrows mark the lifts that also halve the cell, two of which return the same type on the smaller cell. p1 lifts only to p2, the rectangular groups to pmm, pmg and cmm, the square ones to p4g and p4m, and p3 to four different groups. Three groups, outlined, cannot be lifted at all without a special metric: p2, pmm and p6m. The classification

Where a symmetric motif lifts the group

A motif with more symmetry than its site asks for can raise the group of the whole pattern — or not, and which one is decided by the site, not the motif. The criterion is one line: a symmetry of the motif survives into the pattern exactly when it normalises the group. Run over every Wyckoff position of the seventeen, it finds twenty-nine of seventy-two where a motif can lift the group, general positions only in the four groups with a direction to slide along, two sites where the same motif gives different groups depending on how it is turned, and seven lifts between groups that halve the cell.

 Seven cubic antiferromagnets, and what a powder of each can say. Seven collinear antiferromagnets on the three cubic lattices, each with the size of its propagation vector's orbit, the number of the forty-eight cubic operations that keep the vector, the kind of every magnetic ring out to a fixed radius, summed from the actual magnetic reflections of one domain, and what a powder pattern can therefore read about the moments' direction. The two whose halving the cubic group keeps are blind in every ring. An orbit of three leaves every ring uniaxial about a cube axis, an orbit of four about a body diagonal, and the body-centred orbit of six leaves rings that read the direction. The cubic chemistry is the same in every row; the propagation vector decides. What symmetry decides

Where a powder goes blind

A neutron sees only the part of a magnetic moment across its path, so each reflection knows which way the moments point. A powder adds up every reflection of a given length, and for a ring with cubic symmetry that sum comes out the same whichever way they point. But the ring's symmetry is not the chemistry's: it is the symmetry the propagation vector keeps, and most cubic antiferromagnets have lost enough of it to be read.

 Every four-colouring of the seventeen, by the group that permutes the colours. The 281 subgroups of index four across the seventeen plane groups, each a colouring of a pattern in four colours that the pattern's symmetries permute transitively, sorted by the permutation group they induce on the colours: ℤ₄ 20, Klein 77, D₄ 164, A₄ 8, S₄ 12. The groups without a three-fold rotation use only the cyclic, Klein and dihedral groups; the five with one use only A₄ and S₄, apart from a single Klein colouring of p6m. The classification

Four colours, five ways to permute them

Two colours can be swapped in one way and three can be permuted in two. Four colours can be permuted transitively by five different groups, and the seventeen plane groups use all five: 281 four-colourings sort into 20 cyclic, 77 Klein, 164 square, 8 tetrahedral and 12 fully symmetric. The last twenty belong to the five groups with a three-fold rotation, and they are the lattice reduced modulo two.

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