Crystallography & Symmetry
patterns derived from their groups
Concept

Superstructure — where it appears

A structure whose repeat is a whole-number multiple of an underlying one, showing extra weak reflections at the positions the larger cell implies. There are exactly n − 1 of them per parent cell, and their intensity is a difference rather than a sum.

Named by 11 essays across 5 fields — each of them below, with the objects they name alongside it.

An antiphase boundary in p4. Where two antiphase states meet. Above the line the species alternate one way and below it the other, so at the boundary two cells of the same species sit next to one another and the ordering is out of step. This is a domain wall with no change of orientation across it: the crystal is not twinned, its lattice is undisturbed, and diffraction sees it only in the width of the superlattice reflections.

The domains a lost translation makes, which nothing optical can see

An ordering transition can leave the crystal class untouched and take away translations instead. The domains that result have the same orientation, the same shape and the same optical properties as each other, and where two of them meet the ordering is simply out of step — a boundary with no change of direction across it and no way to find it except by looking at the ordering itself.

applied · Domains Sublattices of index n in the plane. For each index up to 12: the number of sublattices found by building every Hermite normal form of that determinant, and the number the Dirichlet series ζ(s)ζ(s−1) predicts — the sum of the divisors in the plane, and a longer sum in space. The two columns are computed by routines that share no code, and the figure does not appear at all if any row disagrees.

How many ways there are to thin a lattice

A sublattice of index n keeps one lattice point in n, and there is never only one way to do it. In the plane the number of them is the sum of the divisors of n; in space it is a longer sum; and both are counted here by writing every one of them down.

lattices · Sublattices Which indices have a square sublattice. For each index up to 26: how many sublattices of the square lattice are themselves square, found by testing whether the quarter-turn maps each one onto itself; the same count as a sum over divisors, +1 for each divisor one more than a multiple of four and −1 for each one less; and the ways of writing the index as a sum of two squares. The three agree at every row, which is Fermat's theorem — and it says that 3, 7 and 11 have no square sublattice at all while 5, 13 and 17 have two.

The sublattices that stay square

A sublattice of the square lattice is itself square exactly when its index is a sum of two squares — so index five has two and index seven has none, and which superstructures a surface can form is decided by a theorem of Fermat's about primes.

lattices · Sublattices Two species on one lattice, ordered at index 2. Every position is a lattice point of the parent and none of them has moved. What has changed is which atom sits where: the larger marks are a sublattice of index 2, the smaller ones its other 1 coset, and the outlined cell is the new repeat. The lattice of positions is untouched and the repeat of the contents is 2 times as large, which is the whole of what an ordering transition does and the reason its signature is in reciprocal space rather than in the positions.

The reflections a superlattice adds

Centring a lattice makes reflections vanish. Ordering two kinds of atom onto a sublattice makes new ones appear, exactly n − 1 of them per parent cell, and their intensity is a difference rather than a sum — which is why an ordered alloy of two neighbouring elements can be invisible to X-rays and obvious to neutrons.

lattices · Sublattices What each group leaves distinct. The number of genuinely different ways of putting 2 species on the cells of a 4 × 4 block, for 9 plane groups. Every row starts from the same 65,536 arrangements; what differs is the group identifying them. Each count is Burnside's average of fixed points, and each was required to divide exactly by its group's order.

Counting what a group cannot tell apart

Sixty-five thousand ways of putting two species on sixteen sites; eight hundred and five structures. The difference between those numbers is not a division, because the symmetric arrangements have short orbits — and the count that gets it right is an average of fixed points.

operations · Counting What each group leaves distinct. The number of genuinely different ways of putting 2 species on the cells of a 4 × 4 block, for 9 plane groups. Every row starts from the same 65,536 arrangements; what differs is the group identifying them. Each count is Burnside's average of fixed points, and each was required to divide exactly by its group's order.

Every colour count at once

Eight hundred and five structures is the answer for two species on sixteen sites. For three species it is a different sum, and for four another. Averaging cycle counts instead of fixed-point counts turns the answer into a polynomial — and refining the same average says how many structures there are at each composition, which is the number anybody actually needs.

operations · Counting At which indices a group contains a copy of itself. A filled circle where the group has a subgroup of that index which is the same plane group again. The groups with no rotation past a half-turn take every index — the lattice can be stretched along one direction by any factor. The four-fold groups take the sums of two squares and the three- and six-fold groups take the Loeschian numbers, because a sublattice invariant under a quarter or a third of a turn is an ideal in the Gaussian or Eisenstein integers and its index is a norm. The groups with mirrors take fewer still, and p4g takes only the squares.

The same group in a bigger cell

A subgroup usually gives something up. An isomorphic subgroup gives up nothing but scale — the same plane group again, on a coarser lattice — and the indices at which that is possible turn out to be the values of a quadratic form.

space-groups · Isomorphic subgroups 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.

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.

space-groups · Isomorphic subgroups 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.

space-groups · Landau 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.

diffraction · Disorder Two populations, and neither of them empty. The reflections of a structure in which three quarters of the atoms are paired by a half-cell shift, sorted by the parity of h + k and each class scaled by its own mean. The two histograms have the same shape, which is the point: each class on its own is an ordinary acentric distribution. What differs is the scale — the odd class is a sixth of the even one on average — and no odd reflection is absent, so no extinction rule fires and nothing about the space group is affected.

A translation that is nearly there

Half a structure copied onto the other half by a half-cell shift, with nothing exact about it. No reflection vanishes, so no extinction rule fires — and the test for a centre of symmetry answers yes about a structure that has none.

diffraction · Statistics

Named alongside it

The objects these essays reach for when they reach for this one.

IndexSublatticeAntiphase boundaryGaussian integerHermite normal formKlassengleicheLoeschian numberOrbitPermutationStabiliserSubgroupSum of two squares

All concepts