Crystallography & Symmetry
patterns derived from their groups
Theme

The theme: Symmetry is decidable — page 8

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.
Thirty-two classes, eighteen groups. Every abstract group the thirty-two crystal classes realise, with the classes that realise it. 8 of the eighteen carry more than one class, and the largest collision is the four hexagonal classes that are all the dihedral group of order twelve. Nothing here is looked up: two classes are put in the same row when a search over images of a generating set finds a bijection preserving multiplication, and the search is finite because a generating set is small and the elements it may map to are the ones of the same order. What symmetry decides

Thirty-two classes, eighteen groups

An inversion centre, a mirror and a two-fold rotation are three of the most different things a crystal can have, and they are the same group of order two. Forget the matrices and keep the multiplication table, and the thirty-two classes collapse to eighteen.

 7 cells explain the lines; one of them is right. A line list from a face-centred cubic cell of 5.64 Å, with a realistic error added, handed to a sweep over every cubic cell between 2 and 12 Å in all three centrings. 7 distinct cells explain every line within the tolerance, and each is a genuine solution rather than a numerical accident. The true cell comes top by de Wolff's figure of merit — the last Q over twice the mean discrepancy times the number of lines the candidate says should have been visible — which punishes a candidate for predicting lines nobody saw. That is the whole of what makes indexing decidable in practice: not the arithmetic, which has many answers, but a criterion for preferring one. Symmetry at work

Indexing a powder pattern

A powder pattern is a list of numbers and a cell is six. Getting the second from the first is the first step of every powder study and the one that fails — because the arithmetic has many answers, and choosing between them is a ranking rather than a deduction.

 A lattice placed in the region, and its distance to each special shape. The modular region, with the two special points marked — the square lattice at the top of the arc and the hexagonal one at its corner — and a third lattice placed by reducing its form. The distances are hyperbolic rather than Euclidean, and the choice is forced rather than aesthetic: a distance between lattice shapes has to be unchanged by every change of basis, and the hyperbolic metric is the one defined by being invariant under exactly that group. Writing the same lattice down on three other bases and measuring again gives the same two numbers to the last digit. Lattices

How far one lattice is from another

A crystal that is nearly hexagonal twins where an exactly hexagonal one would not, and 'nearly' does real work in that sentence. Giving it a number needs a distance that no change of basis can move — which forces the geometry to be hyperbolic rather than flat.

 anisohedral: 2 orbits of congruent tiles. A tiling of the plane by 8 copies of one shape per cell of a lattice of index 64, drawn 1 cell across and 8 up, and coloured by which orbit of the tiling's own symmetry group each tile belongs to. The group has 4 operations per cell and 2 orbits: every tile is congruent to every other, and no motion of the whole pattern carries a tile of one colour to a tile of another. Congruence is a fact about the shapes; an orbit is a fact about the pattern, and they are different facts. The classification

One shape, two kinds of tile

A tiling by copies of a single shape looks as though it must be homogeneous — every tile is congruent to every other, so what could distinguish them? The symmetry group can. There are shapes that tile the plane and admit no tiling whose group carries any tile to any other, and the smallest of them has eight cells.

 p4m: 4 and 4. The standard motif — three points in no particular arrangement — repeated by p4m, with each copy coloured by the sign of the area of the triangle it makes. 4 copies have one sign and 4 the other, because the group contains an operation that reverses orientation. A structure built from one enantiomer cannot sit here: the group would put its mirror image in the same crystal. The colours were computed from the coordinates rather than assigned. Into space

The groups a single hand may sit in

A protein is built from one enantiomer of every amino acid, and a crystal of it contains nothing else. That single fact deletes most of the classification at a stroke: any operation reversing orientation would put the other hand in the same crystal. The criterion is one line of arithmetic, and in the plane the enumeration is complete — five of the seventeen.

 The seven groups a uniform field can have. Five of them have an axis and two do not. A cone has every rotation about its axis and mirrors containing it; a cylinder adds the mirror across the axis and the two-folds that go with it; turning either one destroys the mirrors that would reverse the turn. The sphere and the sphere made of something with a handedness are the two with no axis to speak of. Each drawing is the definition: the group is the set of motions leaving the picture unchanged. What symmetry decides

The seven groups a field can have

Every group in this collection so far has been finite, because a lattice forbids the alternatives. A uniform field has no lattice: rotate it about its own axis through any angle at all and nothing has changed. There are exactly seven such groups, and they come out of the same closure argument that turns sixteen frieze candidates into seven.

 21 points, 3 gap lengths. The first 21 multiples of 377/610, marked on a circle of circumference one, together with the point at zero. The 22 gaps between neighbours take 3 distinct lengths — 13/610 (1 of them), 21/610 (9 of them), 34/610 (12 of them). The largest is the sum of the other two: 13 + 21 = 34. Every quantity here is a whole number over the denominator, so nothing is measured. Order without repetition

Three gaps, and never four

Mark the points α, 2α, 3α round a circle of circumference one. They look scattered. The gaps between neighbouring points do not: for every angle and every number of points there are at most three distinct gap lengths, and when there are three the largest is the sum of the other two. That is where a chain with exactly two tile lengths comes from.

 One orbit of p4m, two of p4. The general position of p4m — 8 points in a cell, all equivalent under that group — with each point coloured by which orbit of p4 it belongs to. Losing half the operations does not move a single point; it changes which of them are related, and the one orbit becomes 2. An atom sitting on this position in the parent becomes 2 crystallographically distinct atoms in the child, which may then be different elements, or move independently, or order. Operations

What a position becomes on the way down

Cool a crystal through a transition and it loses operations. Nothing moves — and one crystallographic site becomes two, which is how an ordering transition finds somewhere to put a second kind of atom.

 How many different lattices share a determinant. One bar per determinant: the number of inequivalent integral lattices whose metric has that determinant, which is the class number of the corresponding discriminant. Area does not decide shape — at determinant 1 and 2 there is one lattice each, and by 11 there are four — and the count does not grow steadily either. Each bar is computed twice: once by enumerating the reduced forms directly, and once by reducing every form in a box and collecting the distinct results, which is a search followed by an algorithm rather than a search over answers. The two agree at every bar. Lattices

How many lattices share a determinant

Area does not decide shape. The number of inequivalent lattices whose metric has a given determinant is a class number, computed by enumerating reduced forms — and checked by reducing every form in a box and counting what comes back distinct.

 4_1: which index gives which group. The isomorphic subgroups of a 4₍1₎ screw group, index by index. An index sharing a factor with 4 gives nothing — the translation cannot be written on the new cell at all — and the rest give a screw whose index is the old one times the inverse of p modulo the axis order. So the answer alternates: some indices give the group back and others give its mirror image, and which is which is decided by p modulo the order of the axis. Into space

A bigger cell, and sometimes the mirror

An isomorphic subgroup gives up nothing but scale — the same group again on a coarser lattice. In space the screw axes sharpen the question, and the answer contains a surprise: a cell three times taller holds the group's enantiomorphic partner, so a left-handed screw contains a right-handed one with nothing done to the crystal but a change of description.

 heesch-two: surrounded 2 times. A shape that tiles nothing, with the rings of copies it does accept: the seed in the first colour and 2 coronas of 7 and 16 copies round it. The search that built this finished, so the shape's Heesch number inside this box is exactly 2, and it cost 3,097 placements. Every cell touching a tile of one ring, corners included, is covered by the next. The classification

Surrounded twice over, and covering nothing

A shape that tiles the plane can be surrounded by copies of itself for ever. A shape that tiles nothing cannot be surrounded for ever — but it can be surrounded once, and sometimes twice, and the number of times is a measurement of how much local success a global impossibility permits.

 -2 0 -3 is forbidden and is reached 64 ways. A layer of the reciprocal lattice of Cc: pale spots are reflections the group extinguishes, solid ones are allowed. The path shows a detour — the beam diffracts once at -3 -3 -3 and again at 1 3 0, and the two together send it in exactly the direction a single reflection at -2 0 -3 would. That reflection is forbidden, so intensity arrives where the symmetry said none could. There are 64 such routes to this one spot inside this window alone. How it is known

The absence that fills itself in

A systematic absence is the strongest evidence this subject has: a whole zone of reflections cancelling exactly, for reasons of symmetry rather than of arithmetic accident. The exactness belongs to a model — that the beam scatters once. A beam that has already been diffracted can be diffracted again, and the two events together land where the group said nothing could.

 The whole space of plane lattices, and its corner. Every plane lattice appears exactly once in this picture. Scaling changes no density, so the leading coefficient is fixed at one; reduction then confines the other two to 0 ≤ b ≤ 1 ≤ c, and every lattice has exactly one reduced form. The curves are the levels of constant density, which are parabolas — a density d needs 4c − b² to equal (π/2d)². They crowd toward the corner b = c = 1, which is the hexagonal lattice at π/√12 ≈ 0.9069; the square lattice sits on the left edge at π/4 ≈ 0.7854. The picture is a search over a region rather than over a list, which is what makes the answer a decision: there is nowhere else for a lattice to be. Symmetry at work

The densest lattice in the plane

Which arrangement of equal discs covers the most floor is a question about infinitely many lattices, and reduction turns it into a question about a two-parameter region with a corner. The answer is at the corner, and the argument finishes.

 What a crystal keeps of itself in a field. Each class, with what is left of it when a field is applied along the axis of its own setting. The residual is the intersection of the class with the field's own group, computed on matrices and matched against the thirty-two rather than named by hand. Where the residual is the class itself, the field takes nothing away — and for an electric field those are exactly the polar classes. What symmetry decides

What a crystal keeps in a field

Curie's principle says the symmetry of an effect contains the intersection of the symmetries of its causes. Applied to a crystal in a field that is an intersection of two groups, one of them infinite — and it comes out exactly, class by class, as a subgroup that decides which effects are permitted next.

 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. Symmetry at work

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.

 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. Lattices

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.

 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. How it is known

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.

 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 symmetry decides

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.

 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. Order without repetition

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.

 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. Symmetry at work

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.

 ⟨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. How it is known

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.

 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. Into space

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.

 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. Lattices

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.

 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. What symmetry decides

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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