Theme

The theme: Symmetry is decidable — page 3

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.

The thirty-two, by crystal system. 32 classes in 7 crystal systems. Each column is one crystal system and each cell one class, ordered by the number of operations it holds. Nothing here is tabulated: the classes come from the enumeration and the marking from a character sum over each group.

What symmetry decides

The holohedry is the ceiling

A crystal never has more point symmetry than its lattice. That single containment decides which system a class belongs to, why there are seven systems and not thirty-two, and why a lattice can be more symmetric than the crystal sitting on it — which is the usual case rather than the exception.

The 4₁ screw axis. 1 of the eleven screw axes a lattice permits, each drawn as the helix it is: 4₁. A turn of 2π/n followed by an advance of m/n of the repeat, so that n turns land exactly m cells along. 0 of those drawn are its own mirror image; the rest come in left- and right-handed pairs.

Into space

Turning and climbing at once

A rotation has a fixed point and a screw has none. That sounds like a small difference and it is the reason a space group is not a point group with extra letters, the reason two hundred and thirty is not seventy-three, and the reason a helix can be a crystal.

Which classes can twin by merohedry, and how many ways. Every crystal class, with the number of twin laws its own lattice offers it. The index of the class in the point group of its lattice is the number of orientations available; 25 of the thirty-two have more than one, and the 7 holohedral classes have exactly one — their crystal already has every symmetry their lattice has, so there is nothing left over to twin by. The names along the right are the old mineralogical ones: hemihedral for half, tetartohedral for a quarter.

Symmetry at work

Twenty-five of the thirty-two can twin, and seven cannot

The number of twin laws available to a crystal is the index of its class in the point group of its lattice, minus one. Doing that arithmetic for all thirty-two classes takes a moment and produces a census with a sharp edge on it — the seven classes that cannot twin this way are exactly the seven that already use everything their lattice has.

The general positions of P2₁/c. Space group P2₁/c, number 14, projected down c on a primitive monoclinic cell. 12 general positions, the orbit of a three-point asymmetric motif, each labelled with its height along c and marked with a comma where the operation that produced it reversed handedness.

Operations

One part in however many, and why it is never quite that

A crystal's contents are the asymmetric unit repeated by the group. The unit's volume is the cell's divided by the order of the group — except that it is always a little more, and the excess is exactly the special positions counted whole.

p4 inside p4m, by area. A fundamental domain for p4m beside one for p4, drawn by the same construction on the same grid. p4 sits inside p4m with index 2: it has 8 ÷ 4 = 2 times as few operations to rebuild the pattern with, so it needs 2 times as much of the cell to rebuild it from — measured here at 1.51 times as many samples. The two domains are one region and 2 copies of it, and the ratio between them is the index rather than a coincidence of shape.

Operations

Domains of a subgroup

A group with half the operations needs twice as much of the cell to rebuild the pattern from. That single sentence is the index arithmetic of the whole classification, and it turns the containments among the seventeen into a statement about area.

$The eleven screw axes, enumerated. An n-fold axis admits a screw for every m from 1 to n − 1, so the orders a lattice permits — 2, 3, 4, 6 — give 11 screws in all. Each row shows the fraction of a cell one turn advances, plotted between zero and one. 3 of them are their own mirror image, which happens exactly when m is half of n; the others pair off into left- and right-handed twins.$ Into space

Eleven ways to turn while climbing

Five rotation orders survive the crystallographic restriction, and each of them admits a screw for every whole number of cells its turns can amount to. That is a sum with four terms, and it is why there are eleven screw axes rather than some other number.

A fundamental domain for p6m. One representative from every orbit of p6m, shaded, with the images that tile the rest of the cell. The domain was found by computing orbits rather than by drawing a region, and every sample's orbit was checked to meet it exactly once — so the region has neither a gap nor an overlap.

The classification

Orbifold notation, the shorter language

Fold a pattern up along its own symmetries and what remains is a small surface with marked points. Its shape is a complete name for the group, and reading the name off costs an arithmetic sum that has to come to two.

$The eleven Laue classes. Adjoining the inversion to each of the thirty-two crystal classes collapses them onto 11 groups. Friedel's law says a diffraction experiment sees the crystal and its inverse alike, so this — and not the crystal class — is what a diffraction pattern's symmetry reports. The highlighted symbol in each row is the class that is already its own Laue class, which is to say the centrosymmetric one.$ What symmetry decides

The eleven a diffraction pattern reports

A diffraction experiment cannot tell a crystal from its inverse. So the thirty-two classes collapse to eleven before a single reflection is indexed, and a structure determination begins by answering a different question from the one it was asked.

$p2 in one cell, p4 on average. On the left, a molecule in one orientation at a site whose symmetry is larger than its own: the arrangement has 2 operations and the detector says p2. On the right, the average over the 2 orientations the site offers, which is what a diffraction experiment measures because different cells choose differently and nothing prefers one choice. The average has 4 operations — it is p4 — and every atom in it is present in half of the cells. Both groups are detected from the point sets rather than assumed, and the difference between them is the reason a refined structure can have symmetry no molecule in the crystal has.$ What a lattice forbids

The symmetry of an average

A diffraction experiment measures an average over some 10²⁰ unit cells, and the average of several orientations is more symmetric than any of them. So a refined structure can carry symmetry that no molecule in the crystal has — including, in the worst case, a centre of inversion in a crystal built entirely of one hand.

The twin laws of class 32. The point group of the lattice of class 32 has 24 operations and the class has 6, so it splits into 4 cosets: the crystal itself, and 3 twin laws. Every operation in a block produces the identical second orientation, which is why the block and not the operation is the law.

Symmetry at work

Quartz has exactly three twin laws, and its lattice is why

Class 32 on a hexagonal lattice has index four, so three twin laws and no more. They turn out to be the three the mineralogists named — Dauphiné, Brazil and the combination of the two — and reading quartz's lattice off its class instead of measuring it would have produced one law where there are three.

One lattice, two cells, and the absences the choice creates. The same set of points described on a centred rectangular cell and on its primitive rhombic cell, with what the centred description scatters. Half the reflections vanish, and they vanish because of how the cell was drawn rather than because of anything the crystal does.

Lattices

Why the bigger cell wins

A centred cell has twice the area it needs and crystallography prefers it anyway. The preference is not conservatism — it buys operations that read as whole numbers along the axes, and the price is a set of reflections that vanish for reasons having nothing to do with the crystal.

The h0l layer of P2₁/c. The h0l reflections of P2₁/c out to 4 in each index, with each spot decided by summing the structure factor over the group's operations: 44 survive and 36 vanish identically, whatever the atoms are. The pattern of holes is the condition h0l: l even, read back off the spots rather than imposed on them.

How it is known

The reflections that are not there

A screw axis and a glide plane leave no mark on the intensity of any reflection. What they do is delete some, exactly, for every possible arrangement of atoms — and the pattern of deletions is computed here from the sum a crystallographer writes down, rather than read from a table.

Neumann's principle for elastic constants in mmm. Each bar is one operation's contribution to the character of the representation the elastic constants live in — the stiffness of the crystal in every direction and shear. The identity contributes the unconstrained count of 21; every other operation of mmm subtracts from it, and the average over all 8 is 9, which is how many independent components the property may have. The sum is exact in integers and is taken in the lattice basis, so no Cartesian frame is chosen anywhere in it.

What symmetry decides

Neumann's principle, as one sum

A physical property of a crystal must be unchanged by every symmetry the crystal has. That is a whole subject in one sentence, and it reduces to arithmetic: how many independent components a property may have is a character averaged over the point group, exact in integers.

$p3, single and twinned. Left, the diffraction pattern of a single crystal of p3. Right, the same crystal twinned, with 50 per cent of it in one orientation. Not one spot has moved — the twin law is a symmetry of the lattice, so the two reciprocal lattices lie exactly on top of one another — and 72 of the 81 reflections drawn have changed intensity. At a fifty-fifty twin the pattern acquires the full symmetry of the lattice's point group and is indistinguishable from a crystal that genuinely has it.$ Symmetry at work

A merohedral twin moves no spot at all

The twin law is a symmetry of the lattice, so the two individuals have reciprocal lattices lying exactly on top of one another. Nothing splits, nothing appears in a new place, and the only thing that changes is that pairs of intensities which were different have been averaged — which produces a diffraction pattern with a symmetry the crystal does not have and no sign that anything is wrong.

$A structure, and the vectors between its atoms. On the left, 4 atoms in a cell. On the right, every one of the 16 vectors between them, each drawn from a common origin: 13 distinct positions, with the 4-fold peak at the origin being each atom paired with itself. That right-hand picture is what a Patterson map shows, and it is the thing a diffraction experiment gives without phases. It has more peaks than the structure has atoms — n² against n — which is why interpreting one is hard, and why it is always symmetric about its centre.$ How it is known

The map that needs no phases

A diffraction experiment measures intensities and loses phases, so the electron density cannot be computed from it. One map can be: the transform of the intensities, whose peaks are not atoms but the vectors between them — every ordered pair, brought to a common origin.

Neumann's principle for elastic constants in 6/mmm. Each bar is one operation's contribution to the character of the representation the elastic constants live in — the stiffness of the crystal in every direction and shear. The identity contributes the unconstrained count of 21; every other operation of 6/mmm subtracts from it, and the average over all 24 is 5, which is how many independent components the property may have. The sum is exact in integers and is taken in the lattice basis, so no Cartesian frame is chosen anywhere in it.

What symmetry decides

A character does not know its basis

The number of independent elastic constants a hexagonal crystal has is computed here from integer matrices in a lattice basis, having never chosen a Cartesian frame. That looks wrong the first time: a physical tensor lives in an orthonormal frame and these matrices are not orthogonal.

Lattices

Twenty-five cells, and fourteen lattices

The usual picture of the fourteen Bravais lattices is a plate of fourteen boxes, which is the answer with the argument removed. The argument is one question asked of twenty-five candidates, and the question has a computable answer.

m3̅m → 4mm: 6 domain states. The transition from class m3̅m to class 4mm loses 40 of the parent's 48 operations, so the child has index 6 and the crystal comes apart into 6 domain states. Each colour is one state — one coset of 4mm in m3̅m — and each holds the same 8 poles. The lost operations are what carries one state onto another, and they survive in the crystal as the relation between its domains rather than as symmetries of any part of it. The descent changes the crystal system, so the states differ in shape as well as in orientation and the transition is ferroelastic.

Symmetry at work

How many domains a transition makes is an index

Cool a crystal through a symmetry-lowering transition and it has to choose one of several equally good low-symmetry arrangements. Different parts of it choose differently, and the number of available choices is the index of the new group in the old one — a number available before any crystal is grown, and one of the few predictions in this field that is a count rather than a bound.

$What each group extinguishes. The extinction conditions of 9 space groups, each derived by summing the structure factor over that group's own operations and reading the surviving rule off the result: P1 — nothing; P1̅ — nothing; P2 — nothing; Pm — nothing; P2/m — nothing; P222 — nothing; Pmm2 — nothing; P4 — nothing; P23 — nothing. 9 of the 9 extinguish nothing at all, and diffraction alone cannot distinguish those from each other.$ How it is known

Where the experiment runs out

Absences narrow the space group down and often not to one. Two groups can extinguish exactly the same reflections and scatter with exactly the same symmetry, and telling them apart needs something the diffraction pattern does not contain.

The symmetry elements of Ccmm. Space group Ccmm, number 63, projected down c on a C-centred orthorhombic cell. The symmetry elements drawn: 4 2-fold rotation axes, 6 glide planes, 12 2₁ screw axes, 2 mirror planes, 8 inversion centres. 2 kind(s) of element in this group have no line or mark in a projection down c — an axis at an angle to the page, or a plane lying parallel to it — and are not in the picture.

Into space

The operations nobody put in

A group is not a list of generators. Compose two of them and something arrives that neither contained — a screw where there were only mirrors, a glide where there was only a mirror and a centring vector — and in three dimensions most of a group's operations get there this way.

Why seven — all 16 candidates. Every subset of the 4 extras available on a strip, closed under composition and named from the operations that come out. 16 candidates give 7 distinct groups: 9 of them generate operations they were not given and land on a group already listed.

The classification

Why sixteen become seven

Four extra operations give sixteen combinations and seven groups. The nine that vanish are not cases anybody forgot — each one comes back from the closure holding something it was never given, and one of them changes the lattice underneath it.

P2₁2₁2₁: the sections its symmetry forces. The Patterson cell of P2₁2₁2₁ with the sections marked. Each operation (M, t) sends an atom at x to Mx + t, so the vector between them is (I − M)x − t; where I − M is singular that vector cannot leave a plane, and the plane's equation comes from the left null space in integers. This group has 3 such operations, giving the sections w = 0.5, u = 0.5, v = 0.5. A heavy atom's vector to its own image is somewhere on one of them, which is what made structure solution possible before computers: a plane can be searched by eye and a volume cannot.

How it is known

Where symmetry stacks the vectors

A Patterson map of a real structure is a blur with thousands of overlapping peaks. A screw axis rescues it: the vectors between symmetry-related atoms cannot leave a plane, so the search for a heavy atom is a search of a section rather than of a volume — and which plane it is falls out of the operation's matrix in integers.

P2₁/c under every cell choice. One group, described in each of the 6 bases that keep its cell the shape its system requires, with the symbol derived from the operations each time. The distinct symbols are P2₁/c, P2₁/a, P2₁/n — 3 names for one group. Nothing about the crystal has changed: the basis changes all have determinant ±1, so the lattice is untouched, and the census of rotations, screws, mirrors and glides is identical in every row, since conjugation cannot turn one kind into another. What changes is which lattice vector a glide's translation is half of, and the glide letter names exactly that.

Into space

One group, three symbols

P2₁/c, P2₁/a and P2₁/n are the same space group written on three choices of axes, and the literature contains all three as though they were different. Deriving a symbol from a group's own operations shows why — and found an entry on this site that had been carried under another setting's name for two phases.

Everything class m3̅m can descend to. The 25 crystal classes that are subgroups of m3̅m, arranged by order, with the 56 maximal steps between them drawn as edges. The order of each row is printed down the left, so the index of any step is the ratio of the two rows it joins. A symmetry-lowering transition can only be continuous when it goes down one of these edges, and the index on the edge is the number of domain states the transition produces. A descent of several steps is possible but has to happen discontinuously or through the intermediate classes.

Symmetry at work

The descent of symmetry is a lattice, not a tree

Which classes a crystal can fall to when it loses symmetry, drawn as a graph with the index on every edge. It is routinely called a tree and it is not one — a class can be reached from its parent by several different routes of the same total index, and which route a material takes is a physical question the diagram deliberately leaves open.

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