Crystallography & Symmetry
patterns derived from their groups
Concept

Centrosymmetric — where it appears

Having an inversion centre, so that every atom at a position has a partner at its negative. Whether a structure is centrosymmetric is not decidable from any single reflection, and the distribution of all of them is what settles it.

Named by 7 essays across 2 fields — each of them below, with the objects they name alongside it.

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.

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.

point-groups · Diffraction 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.

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.

diffraction · Diffraction What the inversion does to three sums in 4/mmm. The 16 operations of 4/mmm come in pairs — every operation together with its own negative, because the class contains the inversion — and each row pairs the two terms they contribute. For an even-rank polar property the pair is two equal bars: the inversion changes an even number of indices and the character cannot see it, so the average is whatever it was before the inversion was added. For an odd-rank polar property and for an axial one the pair is a bar and its reflection, and the sum is exactly zero — which is why piezoelectric moduli and gyration tensor are forbidden here outright rather than merely small. Neither statement is about this class: the cancellation is checked over all 11 centrosymmetric classes and all four odd or axial properties every time this figure is drawn.

Twenty of the twenty-one

Twenty-one crystal classes have no centre of symmetry, and twenty of them permit piezoelectricity. The exception is 432, which has twenty-four operations, no inversion, and a character sum that cancels to nothing — and the reason it fails is not that it has too much symmetry in any ordinary sense.

point-groups · Properties N(z): the fraction of reflections weaker than z. The cumulative distribution of normalised intensities, measured on two structures built from the same atoms — one with an inversion centre, one without — and drawn against the two closed forms, 1 − e^(−z) without a centre and erf(√(z/2)) with one. The curves are furthest apart at small z, which is the useful end: a centrosymmetric structure has far more nearly-absent reflections, because its structure factor is a single real number that can pass through zero rather than a complex one that rarely does.

Whether there is a centre is a statistic

Everything else on this site is decidable: a pattern has a symmetry or it does not, and the detector settles it in integers. Whether a structure has an inversion centre is not like that. No single reflection carries the answer — the distribution of all of them does.

diffraction · Statistics 15 classes may rotate light, 11 of them chiral. A crystal is chiral when its point group contains no improper operation, and there are 11 such classes. A crystal may rotate the plane of polarisation when its class permits a non-zero gyration tensor, and there are 15. The four in the difference — 4̅, m, 4̅2m, mm2 — are achiral and may still rotate light, which is why the two words are not synonyms. In each of the four, symmetry forces the tensor to be traceless, so the rotation changes sign with direction and cancels in any average over directions.

Fifteen may rotate light, and eleven are chiral

Optical rotation and handedness are treated as the same thing and are not. Eleven crystal classes are chiral; fifteen permit a crystal to rotate the plane of polarisation; and the four in between are the reason quartz and sodium chlorate are the examples everybody uses.

point-groups · Optical The same structure, mapped from intensities and from differences. Left, the ordinary Patterson map of the structure: 14762 interatomic vectors, a continuous field of overlapping peaks, and the two vectors between the anomalous scatterers — circled — nowhere among its strongest. Right, the map from squared Bijvoet differences over the same reflections: two peaks after the origin, and they are those two vectors. The difference map is 7381 times smaller a problem to read.

A map of the atoms that break the law

Feed a Patterson synthesis the differences between the two halves of each Friedel pair instead of the intensities, and the map that comes back holds the vectors between the anomalous scatterers and nothing else. Two atoms among a hundred and twenty-two: 14,762 vectors become two.

diffraction · The Patterson function Two symmetric structures a diffraction pattern cannot separate. Two arrangements of 6 atoms on a 6 × 6 torus, each invariant under the plane group p6m, drawn beside the Patterson they share. No translation and no inversion carries one onto the other, so they are different structures; every one of the thirty-six interatomic vector counts is the same, so every diffracted intensity is the same and no measurement at any resolution separates them. Of the 4 structures with this symmetry and this many atoms, there are only 3 Pattersons — so imposing the most symmetric of the seventeen plane groups has not removed the ambiguity.

Symmetry does not rescue a Patterson

Every homometric pair found so far sits on a bare ring with no operations imposed, and a real crystal sits in a space group. Impose one and the ambiguity does not go away: 12 of the 13 groups searched still have pairs, and at six atoms the hexagonal groups are indistinguishable two to three times as often as the general position.

diffraction · Homometry

Named alongside it

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

Friedel lawStructure factorAnomalous scatteringCharacterCrystal classLaue classNeumann principleThe Patterson functionAxial tensorBirefringenceCentral limit theoremChirality

All concepts