The collection

Every essay — page 19

One idea per essay, ordered so that the earlier ones set up the later ones — but nothing here depends on being read in sequence.

What symmetry decides

Thirty-two classes, enumerated rather than listed — and then the one thing they are for outside crystallography's own bookkeeping: which components of a physical property a crystal is permitted to have before anybody measures it.

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.

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.

Lattices

The repeating scaffold underneath every crystal. Five in the plane, fourteen in space, and no others — a classification with a short proof.

In eight dimensions one lattice wins at every width

In space no lattice has the smallest Gaussian sum at every width, because the densest lattice wins when the Gaussian is narrow and its dual wins when it is wide, and fcc is not bcc. The argument fails exactly when the densest lattice is its own dual. In eight dimensions it is: E₈, with 240 shortest vectors, beats D₈, its dual, the cubic lattice and a sum of two four-dimensional lattices at every width tried, by a factor of at least 1.31, and its sum is mirror-symmetric in the logarithm of the width.

The classification

Exactly seventeen ways to fill the plane with a repeating pattern. Not a fact to memorise: a theorem, with a finite argument and no eighteenth case.

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.

Order without repetition

Penrose tilings and quasicrystals — patterns with long-range order, five-fold symmetry, and no repeating cell at all.

Every vertex of a Penrose patch, by the symmetry of what lies within three edges of it. A region of a Penrose rhomb tiling 15.2 edges across. Each vertex is marked by the local group of the patch of radius 3.05 edges about it: a short line along the mirror where that patch has one (98 vertices), a large dot where it has a five-fold centre (7), and a small dot where it has no symmetry at all (118). The mirrors are common and point in the tiling's ten directions; the five-fold centres are rare; nothing has a half-turn.

Five-fold centres stay few, and mirrors do not

The Fibonacci chain has one palindrome of every even length and two of every odd length, for ever. Run the same census on the patches of a Penrose tiling and the plane gives three different answers at once. Patches with a five-fold centre stop at four, however large they are drawn. Patches with a mirror grow in number with their radius, by about fifty for every edge. And no patch wider than a single tile has a half-turn at all. What decides which answer an operation gets is the size of the set it leaves fixed in internal space.

What symmetry decides

Thirty-two classes, enumerated rather than listed — and then the one thing they are for outside crystallography's own bookkeeping: which components of a physical property a crystal is permitted to have before anybody measures it.

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.

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.

Lattices

The repeating scaffold underneath every crystal. Five in the plane, fourteen in space, and no others — a classification with a short proof.

Almost every descent ends at D₄. At five widths of the Gaussian, twelve local minimisations of the lattice sum over all four-dimensional lattices of unit covolume, each from a random lattice, each marked by where it ends and labelled with the number of shortest vectors of the lattice it ends at. Fifty-nine of the sixty end at D₄, with twenty-four shortest vectors. One, at the widest Gaussian, ends at A₄*, with ten, a lattice whose sum is higher than D₄'s but which no small change lowers.

The two lattices where a four-dimensional descent stops short

In four dimensions the argument that rules out a single best lattice in space has nothing to act on, so whether one lattice wins at every width is left to be measured. A search over every four-dimensional lattice finds D₄ from almost anywhere. The exceptions are the finding: two lattices, A₄ and its dual, where a descent can stop short, each at one end of the widths and neither in the middle, for the same reason Voronoi found four dimensions has two perfect forms.

The classification

Exactly seventeen ways to fill the plane with a repeating pattern. Not a fact to memorise: a theorem, with a finite argument and no eighteenth case.

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.

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.

Order without repetition

Penrose tilings and quasicrystals — patterns with long-range order, five-fold symmetry, and no repeating cell at all.

Patches of an icosahedral quasicrystal grow with the dimension their symmetry fixes. The number of distinct patches about a vertex of the canonical icosahedral quasicrystal that keep a given symmetry, against the patch's radius in edges on logarithmic axes, counted per axis or per mirror plane: along a five-fold, a three-fold and a two-fold axis, and across a mirror plane. The axes' counts grow in proportion to the radius and the mirror's as its square, the slopes given are the last four points'. Along the bottom, the patches with an inversion centre: one up to a radius of 1.9 edges, and none from 2.15 on.

In space, a five-fold axis is a line

In a Penrose tiling the patches with a five-fold centre stop at four, however large they are drawn, because a five-fold rotation fixes only a point of the tiling's internal space. Slice a quasicrystal from six dimensions instead of four and the internal space has three dimensions, where a rotation fixes a whole line. The five-fold patches of the icosahedral quasicrystal then grow in number with their radius, from five to forty-six per axis, while the patches with a centre of inversion, which fixes only a point, vanish past two edges. Counting them takes internal space: a sample of vertices cannot.

Into space

Seventeen becomes two hundred and thirty. Screw axes, glide planes, and the translations that no choice of origin can remove — the operations a flat surface has no room for.

Cutting a sheet can give it a hand

Cut a periodic sheet along a line and the edge that is left has a symmetry of its own: a frieze group, drawn in the plane across the cut. A chiral sheet can only have chiral edges. An achiral one usually has chiral edges too, in all but a few directions — and eight of the eighty layer groups have no achiral edge at all, however the sheet is cut.

Lattices

The repeating scaffold underneath every crystal. Five in the plane, fourteen in space, and no others — a classification with a short proof.

The centrings each holohedry allows, prime by prime. For each of the seven holohedries on its conventional lattice and each prime from 2 to 7, how many of the lines and planes of the lattice reduced modulo that prime the holohedry leaves invariant, and which of them give a lattice other than the one being centred. At 2 they give C for the monoclinic system, C, I and F for the orthorhombic, I for the tetragonal and I and F for the cubic; at 3 they give the rhombohedral lattice from the hexagonal one; at 5 and 7 nothing new.

Only two and three can centre a lattice

The centring letters P, A, B, C, I, F and R are usually a list brought to the Bravais lattices. They can be derived instead: a centring is a subspace of the lattice reduced modulo a prime, and a centring that keeps a crystal system's symmetry is a subspace its holohedry leaves invariant. Enumerating every one for the seven holohedries and the primes up to seven gives exactly the fourteen, with new lattices only at two and three. The reason is the crystallographic restriction, one step removed: every holohedry has an order made of twos and threes.

The classification

Exactly seventeen ways to fill the plane with a repeating pattern. Not a fact to memorise: a theorem, with a finite argument and no eighteenth case.

The seventy-five rod groups by what fixes the axis and what moves along it. Every rod group sorted by its kernel, the plane point group of operations that leave every point of the axis in place, and by the group of the line it maps onto: translations only, or translations and reversals. Each chip counts the rods with that kernel, that line group and a given number of steps to the repeat. 29 never reverse the axis and 46 do, seventy-five in all, derived from the kernel and the rule that joins it to the line and agreeing cell by cell with the rods counted class by class.

Seventy-five is twenty-nine and forty-six

The eighty layer groups came out as a plane group with a sign on each operation. The seventy-five rod groups have an account of the same shape turned round: a finite group of the plane across the rod, which is what leaves the axis alone, extended by a group of the line, which is what moves along it. Twenty-nine rods never turn their axis over and forty-six do, and the count comes out cell by cell as the rods counted class by class. The screw of a rod is the turn its smallest step gives the plane, and the kernel decides its subscript.

Order without repetition

Penrose tilings and quasicrystals — patterns with long-range order, five-fold symmetry, and no repeating cell at all.

$The second-order satellites alone cannot measure the curvature of a size effect. The Cramér–Rao error in the quadratic size coefficient ε₂, as a fraction of its true value, from six sets of satellites of a modulated chain of 30,000 sites with 2% intensity error, and the correlation between the errors in ε₂ and the linear coefficient ε₁. From second-order satellites alone the error is thousands of times ε₂ at one reflection and still a hundred times it at three, with the two coefficients correlated at 1.000. With the first-order satellites added, one reflection gives ε₂ to about a third of itself and three to about a tenth.$

The second order cannot see a curved size effect alone

When the spacing between atoms depends on composition along a curve rather than a line, the displacement of a modulated chain gains a second harmonic, and the second-order satellites should measure it. They cannot do it on their own. At every reflection a second-order satellite sees the straight part and the curved part of the size effect in almost the same proportion, so adding reflections adds copies of one equation. The first-order satellites, which see only the straight part, are what separates them.

How it is known

A crystal's structure is read from the pattern it scatters. The reciprocal lattice, systematic absences, and what an experiment can and cannot see.

Heavier atoms spoil the line, and then mend it. Above, the scatter of Sayre's ratio about its fitted line, averaged over four random cells, as a quarter of the atoms is made heavier, for cells of eight and of twelve atoms. Below, one minus the square of ρ, the correlation between the density's transform and its square's, computed from the composition alone. The spread of atomic numbers grows without limit along this axis, but ρ does not keep falling: it is lowest near a weight of three and climbs back towards one as the heavy atoms come to dominate, because a cell ruled by a few equal heavy atoms is nearly a cell of equal atoms. The scatter rises and falls with it. At equal weight what scatter remains comes from atoms that overlap, more of them in the larger cell.

Unequal atoms break the equality, and very unequal ones mend it

Sayre's identity is exact for a cell of equal atoms. Give a quarter of them more weight and the line it predicts scatters, reflection by reflection, by exactly the difference between weighting atoms by Z and by Z squared. Make them heavier still and the scatter shrinks again, because a cell ruled by a few heavy atoms is nearly a cell of equal ones. The scatter measures the cell, but only if the phases are already known.

Into space

Seventeen becomes two hundred and thirty. Screw axes, glide planes, and the translations that no choice of origin can remove — the operations a flat surface has no room for.

A ribbon can be achiral where its edges are not

Cut an achiral sheet once and the edge is usually chiral, in almost every direction. Cut it twice, into a ribbon, and the ribbon may be achiral even when both its edges are chiral, because an operation can carry the ribbon onto itself by exchanging the edges — but only if the ribbon's middle line sits on a centre of inversion or a mirror parallel to the cut. Seven of the eight sheets with no achiral edge give achiral ribbons, and one achiral sheet gives nothing but chiral strips however it is cut.

Lattices

The repeating scaffold underneath every crystal. Five in the plane, fourteen in space, and no others — a classification with a short proof.

The centrings six four-dimensional lattice groups allow, prime by prime. For each of the six four-dimensional lattices whose symmetry groups are maximal, with the group's order, and each prime from 2 to 7: the subspaces of the lattice modulo that prime the group keeps, sorted by what centring by each one makes. New Bravais types appear only at 2, three of them, all over the cube-and-line lattice, and at 5, where A₄ centred by fifths is A₄*. Both centrings of the hypercubic lattice by halves make D₄, which has three times the symmetry.

The body-centred hypercube is the checkerboard lattice

In three dimensions the centring letters come out as the subspaces a holohedry keeps modulo a prime, and only two and three make new lattices. In four dimensions the same census, run on the six lattices whose symmetry groups are maximal, finds a prime that the three-dimensional argument never could: five centres A₄ into its dual. It also finds that the most familiar centring does not survive the extra dimension. The body-centred hypercubic lattice is not a centred hypercube at all: its body centre is exactly as far away as an edge, and it is D₄, with three times the symmetry.

The classification

Exactly seventeen ways to fill the plane with a repeating pattern. Not a fact to memorise: a theorem, with a finite argument and no eighteenth case.

Ninety-six four-colour designs. For each of the seventeen plane groups, the number of its four-colourings, as subgroups of index four, and the number of distinct designs they fall into under the affine normaliser, sorted by the group that permutes the four colours. The 281 colourings make 96 designs: 13 ℤ₄, 39 Klein, 39 D₄, 2 A₄, 3 S₄.

Ninety-six four-colour designs

The seventeen plane groups have 281 four-colourings, counted as subgroups of index four, and many of them are the same design described from a different origin, on different axes or from a neighbouring cell. Identified under every affine map that carries the pattern's group to itself, they make ninety-six designs. The same computation run at two and three colours gives forty-six and twenty-three, and all three numbers match the classical counts of coloured plane groups.

Order without repetition

Penrose tilings and quasicrystals — patterns with long-range order, five-fold symmetry, and no repeating cell at all.

$What each kind of satellite of a two-wave chain says about the curvature of the size effect. The Cramér–Rao error in the quadratic size coefficient ε₂, as a fraction of its true value, from seven sets of satellites of a chain modulated by two incommensurate waves, with 2% intensity error: with the two modulation amplitudes refined as well (upper bar of each pair) and with them known (lower bar). The sum or the difference satellites alone say almost nothing either way. Together, with the amplitudes known, they fix the curvature to under one per cent from a single reflection; with the amplitudes free they do not, and adding the first-order satellites, which fix the amplitudes, restores it.$

Two waves measure the curvature one wave hides

A chain modulated by one wave cannot tell a curved size effect from a straight one at second order: every second-order satellite sees the two in the same proportion. Modulate it by two incommensurate waves and the curvature puts the product of the waves into the displacement, at their sum and at their difference. The satellites there see the curvature with opposite signs. Two equations of opposite sign separate two unknowns, and once the two waves' amplitudes are known, the mixed satellites of a single reflection fix the curvature to under one per cent.

What symmetry decides

Thirty-two classes, enumerated rather than listed — and then the one thing they are for outside crystallography's own bookkeeping: which components of a physical property a crystal is permitted to have before anybody measures it.

Which way a fibre of achiral crystals rotates light. For three achiral classes that permit a gyration tensor, every crystal direction that could be aligned along a fibre texture's axis, drawn on a disc as seen from above the z axis, and shaded by the sign of the rotation the texture then shows along its axis. In each class the rotation takes both signs, in regions separated by a cone on which it vanishes. For 4̅2m and mm2 that cone is exactly the class's mirror planes, where the texture inherits a mirror and must be inactive; for 4̅, which has no mirrors, the cone is where the rotation passes through zero between a right-handed texture and a left-handed one.

A fibre of achiral crystals can rotate light

Four achiral crystal classes permit optical rotation, of both signs in different directions. Grind such a crystal into a random powder and the rotation averages away completely. Align the grains along one direction and it comes back: the texture rotates light along its axis exactly as one grain does, half as much the other way across it — and the direction chosen for the alignment decides the texture's hand.

How it is known

A crystal's structure is read from the pattern it scatters. The reciprocal lattice, systematic absences, and what an experiment can and cannot see.

The heavy atom the flipping solver cannot see past

Sayre's identity degrades as a cell's atoms become unequal, most of all for a quarter of heavy atoms three times the weight of the rest, and the obvious prediction is that a solver built on the same sparseness should struggle there too. It does not. Charge flipping solves a cell of carbon with sulphur in it more often than carbon alone, and never solves a cell with one lead atom — because a threshold stated in standard deviations belongs to whichever atom owns the map's variance.

Into space

Seventeen becomes two hundred and thirty. Screw axes, glide planes, and the translations that no choice of origin can remove — the operations a flat surface has no room for.

Two hundred and twelve of the 219 are made of their own operations. The 219 affine space-group types divided by which of their own operations generate them, lattice translations included. 110 are generated both by their screws and glides alone and by their rotations, mirrors and inversions alone; 67 by their screws and glides only; 29 by their point operations only; 6 only by the two kinds together; and 7 by nothing they contain — P1, P2, Pm, Pmm2, P4, P3, P6 — which need a translation given outright.

Seven space groups cannot make their own translations

Every space group contains a lattice of translations, and for all but seven of the 219 types those translations are products of the group's other operations. A screw done twice climbs its axis and a glide done twice slides along its plane, so the non-symmorphic operations make lattices by themselves. The seven that cannot are exactly the seven plane groups with no glide, repeated along a line they all fix, and the reason is a difference between a glide line and a glide plane.

The classification

Exactly seventeen ways to fill the plane with a repeating pattern. Not a fact to memorise: a theorem, with a finite argument and no eighteenth case.

$Two hundred and thirty groups on a hundred and twenty-two diffraction symbols. Every space group placed in a column for its diffraction symbol — Bravais lattice, Laue group and systematic absences — with the columns grouped by lattice. There are 122 symbols. 50 of them name one group; 44 are shared by two, 23 by three, 2 by four and 3 by five.$

Every ambiguity in a diffraction pattern, sorted by its cause

A diffraction pattern shows a lattice, the symmetry of its intensities and the reflections that are missing, and the 230 space groups show 122 different combinations of the three. Fifty of those name a single group. For the rest, each pair of groups that share one can be sorted by why they do, and there are five reasons. Four of them are ambiguities some further measurement resolves. The fifth, two groups with the same operations in the same places except for where their axes cross, happens exactly twice, and nothing but a solved structure decides it.

Order without repetition

Penrose tilings and quasicrystals — patterns with long-range order, five-fold symmetry, and no repeating cell at all.

At the sum of all three wavevectors the cubic and the quadratic paths nearly cancel. The intensity of the satellite at h + q₁ + q₂ + q₃ for the first four reflections, computed with only one size coefficient switched on at a time and with all three. The cubic coefficient alone gives about 3 × 10⁻⁷ at h = 1, the quadratic alone about 2 × 10⁻⁷, the linear alone less than 10⁻¹⁰. With all three the satellite is ten times weaker than with the cubic alone, because the cubic term's displacement and the quadratic term's pair harmonic times a first-order wave arrive with opposite signs.

Three waves measure the cube through the slope

A size effect that bends twice puts the product of three modulation waves into the displacement, at the sums and differences of all three wavevectors, and nowhere else does a cubic term reach so directly. The satellites there were expected to measure it. They see it, but the strongest of them is ten times weaker than the cube alone would make it, because the quadratic term arrives at the same place with the opposite sign, and against any realistic background they say nothing. The cube is measured instead by the strongest satellites of all, the first-order ones, because it makes each wave's slope depend on how strong the other two waves are.

How it is known

A crystal's structure is read from the pattern it scatters. The reciprocal lattice, systematic absences, and what an experiment can and cannot see.

Diffuse scattering gathered under every Bragg peak. The one-phonon thermal diffuse scattering of a square lattice with springs to nearest and next-nearest neighbours, over the reciprocal plane from minus 2.5 to 2.5 in each index, with the Bragg reflections marked. The intensity rises as one over the squared distance to every reflection, because the acoustic phonons' frequencies vanish there, and it grows with the square of the scattering vector, so the lobes are strongest far from the origin. The lobes are not round: a small step from (1,0) along k gives 2.7 times the intensity of the same step along h, because it probes transverse phonons, which are softer, and that ratio is what an experiment reads the elastic constants from.

A warm plane crystal has no Bragg peaks

Thermal motion is disorder that moves, and in space it costs a crystal a little of each Bragg peak and gathers it into diffuse scattering underneath. In a plane it costs more than a little. Computed exactly from the phonons of a harmonic square lattice, an atom's mean-square wandering grows by the same amount every time the crystal doubles in size, so no Debye–Waller factor survives, and every Bragg peak fades as a power of the crystal's size — a power proportional to the temperature times the square of the reflection's distance from the origin.

What symmetry decides

Thirty-two classes, enumerated rather than listed — and then the one thing they are for outside crystallography's own bookkeeping: which components of a physical property a crystal is permitted to have before anybody measures it.

A looser fibre with more longitudinal response. The three piezoelectric coefficients of a polar fibre of grains with d33 = 90, d31 = −33 and d15 = 560 pC/N, as the tilt spread grows from nothing to a uniform one, with the degree-one and degree-three parts of d33 dashed. The degree-one part is 265 and the degree-three part -175; the negative octupole decays faster, so d33 rises from 90 to 168 at a spread of 30° before falling to nothing.

A looser fibre, more piezoelectric

Spread the grains of a fibre about its axis and every property decays, but not at one rate: each spherical harmonic a property is built from is multiplied by its own average, and the higher the degree the faster it goes. A property made of two degrees therefore changes shape as the fibre loosens. For a polar grain whose shear coefficient dwarfs its longitudinal one, the fibre's longitudinal response nearly doubles before it falls; for another, a shear coefficient changes sign.

By idea · By group · By object · Search