Crystallography & Symmetry
patterns derived from their groups
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The theme: The same arithmetic, renamed — page 4

A crystal form is an orbit. A twin law is a coset. The domain states left by a phase transition are the cosets of the low-symmetry group in the high-symmetry one. Four subjects that grew up in different centuries and different departments, doing one piece of arithmetic under four names.
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.

 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. Order without repetition

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.

 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. What symmetry decides

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.

 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. Symmetry at work

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.

 [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. Symmetry at work

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.

 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. How it is known

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.

 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. What symmetry decides

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.

 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. Order without repetition

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.

 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. How it is known

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.

 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. How it is known

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.

 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. Into space

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.

 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. What symmetry decides

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.

 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. How it is known

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.

 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. What symmetry decides

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.

 How many constants a texture permits. Every one of Curie's seven groups against every property this collection computes, as the number of independent components each permits. The counts are averages of a character over an infinite group, which is exact because the character is a trigonometric polynomial: the average is its constant term. A poled ceramic is the row ∞m, with one pyroelectric coefficient, two dielectric constants, three piezoelectric moduli and five elastic ones — and a zero for optical activity, which the mirrors forbid. What symmetry decides

What a texture permits

A poled ceramic has no lattice, no cell and no class, and yet the number of piezoelectric moduli it may have is exactly three. The group is one of Curie's, the average over it is an integral, and the integral turns out to be a single Fourier coefficient — which is why the answer is exact and why a texture is indistinguishable from a hexagonal crystal until rank six.

 A screw dislocation of Burgers vector 1, after 40 steps of growth. The height of a growing surface, light for low and dark for high, over a patch 25 cells across with a screw dislocation at its centre. Growth is an integer rule — a site rises when it has a neighbour a layer higher — and the only thing that makes this patch different from a flat one is a branch cut along which the comparison is offset by the Burgers vector. The step winds round the centre instead of running out: after 40 steps the centre has climbed 10 layers and the surface is still growing at 110 sites a step. The shading is normalised to the patch's own range, so the shape is the steady state the mechanism predicts and is the same at every step count; the numbers at the foot are what changes, and they are what the claim of unending growth is actually about. Symmetry at work

The step that never runs out

A perfect crystal face cannot grow: an atom arriving on a flat plane touches it on one side and leaves again. Faces grow anyway, and the reason is a defect — a screw dislocation puts a step on the surface that winding round it never consumes.

 6°: a boundary with a dislocation every 9.5 cells. Two crystals of the same lattice, each turned by half of 6 degrees in opposite senses, meeting on the dashed line. Almost everywhere along it the atoms of one side face the atoms of the other at very nearly the right distance — the boundary is good crystal — and at the marked places the misfit has accumulated to a whole lattice vector and an extra half-plane has to be inserted. Those are the edge dislocations, and they are 9.5 cells apart against the 9.6 that Frank's formula gives. Symmetry at work

A small angle is a row of dislocations

Turn one crystal a degree against another and the coincidence arithmetic says they share almost nothing. The boundary between them is nevertheless nearly perfect crystal, and both statements are true: the misfit stays small for a long way and then, all at once, needs an extra half-plane.

 Every wall is a frieze. Each ferroelastic descent, with the frieze group of each of the two walls its domains permit. A wall is periodic along its length and bounded across it, so its symmetry group is one of the seven — the classification this collection derived early as the same argument on a strip, arriving here as a fact about interfaces. The last column counts the operations in the wall's group that exchange the two domains rather than fixing them: a wall is unchanged by having its sides swapped, so those belong to it, and they are why a wall is often more symmetric than either domain. Symmetry at work

The wall has a group of its own

A boundary between two domains is periodic along its length and bounded across it, so its symmetry is a frieze. The seven, derived here early on as an exercise on a strip, turn out to be the classification of interfaces.

 A hundred and thirteen orbit types, merged into shapes. The three counts, and what stands between them. 113 is the number of kinds of form this site publishes: one for every stabiliser a face can have, in every class. Allowing a stratum to change shape along its own family raises it to 164. Merging entries that are the same solid with the same symmetry, wherever they occur, brings it down to 48 — 30 that enclose a volume and 18 that do not, which is the count every mineralogy text prints, with the dome and the sphenoid kept apart rather than merged. The last line is the warning: throwing away the symmetry of the solid and keeping only its combinatorial type leaves 35, because a rhombic dipyramid, a tetragonal dipyramid and an octahedron are one and the same arrangement of eight triangles. Symmetry at work

A hundred and thirteen orbits, and forty-eight shapes

This collection reports 113 kinds of crystal form and every mineralogy text reports 47. That difference was explained here in a paragraph and never computed, which means nobody had checked it. Computing it needs a definition of *shape* a program can decide, and the definition turns out to be the interesting part.

 Every subgroup of index two is normal; at index three most are not. For each of the seventeen plane groups, its abelianisation and the number of normal subgroups of each small index against the number of subgroups of that index. The index-two column is complete every time, because the left and right cosets of a subgroup of index two are the same pair of sets. At index three and four the two numbers part, and the gap is what normality costs: a subgroup that is carried to a different subgroup by some operation of the group it sits in. Operations

The quotient each normal subgroup leaves

Two hundred and eighty-one subgroups of index four across the seventeen plane groups, and ninety-seven of them normal. Which ones, and what is left when they are divided out, needs no enumeration at all: below order six every group is abelian, so a normal subgroup of small index is a subgroup of the abelianisation and its quotient is decided by a product of greatest common divisors.

 A 21.79° twist, and the cell its beat has. Two copies of the same lattice, one turned. The coarse pattern a reader sees is the beat between them, and the outlined cell is computed from the two lattices rather than measured off the picture: the moiré reciprocal lattice is the original acted on by (I − R), so the moiré cell is the original scaled by one over twice the sine of half the twist, and turned through a right angle plus half the twist. Symmetry at work

A beat is not a period

Lay one lattice on another and turn it: the coarse pattern that appears has a spacing anyone can compute, a over twice the sine of half the twist, and it exists at every angle whatever. Whether the superposition actually repeats is a different question with a different answer — countably many angles say yes, and at most of those the true cell is larger than the beat by a definite factor. On a square net it always is.

 The alias accounts for every line and predicts more. The observed lines above, and below them the grid of a supercell that explains all of them. The full ticks are the observed lines, which the alias reproduces exactly; the faint ones are lines the alias predicts and nobody saw. That second set is the only thing that separates the two cells, and it is why an indexing criterion has to charge for unobserved lines rather than measure agreement. Symmetry at work

Every alias is a supercell

A cell that explains every line of a powder pattern is not a near miss and not a coincidence: its reciprocal grid contains the true one, which means its own cell is a superlattice of the true cell. So the ambiguity of indexing is the arithmetic of superlattices, and it can be counted — two cells with one unknown, sixteen with two, sixty-two with three, all of them accounting for the same twenty lines exactly.

 No two cubic grains are more than sixty-three degrees apart. For each proper class: how many rotations describe one misorientation, the largest disorientation there is, and the mean over uniformly random orientations. The maximum is found by sampling and then climbing locally, so it is a lower bound that has stopped moving rather than a solved value — and it lands on the numbers the literature records. Symmetry at work

The angle two grains differ by

A crystal's axes are not labelled, so a relative orientation between two grains has as many descriptions as the symmetry allows — five hundred and seventy-six of them for a cubic crystal — and their rotation angles run from a few degrees to more than a hundred and seventy. The honest answer is the smallest, and its largest possible value is a number: no two cubic grains are more than sixty-three degrees apart, whatever anybody does to them.

 Four angles, and the integer that picks them. Two roots at angle θ have Cartan integers whose product is 4cos²θ. Both are whole numbers and the product is below four, so it is nought, one, two or three — and each value fixes the angle between the two roots, and with it the angle between the mirrors perpendicular to them. The shaded wedge is the region the pair of mirrors folds the plane onto; the smaller it is, the larger the group they generate. What a lattice forbids

Four root systems, and the same four rotations

Two mirrors meeting at an angle generate a group. Ask that the group be finite and that a certain pairing between the mirrors come out a whole number, and the angle has only four possible values — from which the rotations that survive are of order two, three, four and six. The crystallographic restriction arrives with no lattice anywhere in the argument.

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