International
Tables for Crystallography Volume C Mathematical, physical and chemical tables Edited by E. Prince © International Union of Crystallography 2006 |
International Tables for Crystallography (2006). Vol. C. ch. 9.8, pp. 915-937
Section 9.8.3. Introduction to the tables |
In what follows, the tables dealing with the (3 + 1)-dimensional case will be presented. The explanations can easily be applied to the (2 + d)-dimensional case also [Tables 9.8.3.1 and 9.8.3.4].
The (3 + 1)-dimensional lattice is determined by the three-dimensional vectors a*, b*, c* and the modulation vector q. The former three vectors give by duality a, b, and c, the external components of lattice basis vectors, and the products , , and the corresponding internal components. Therefore, it is sufficient to give the arithmetic crystal class of the group and the components σj (σ1 = α, σ2 = β, and σ3 = γ) of the modulation vector q with respect to a conventional basis a*, b*, c*. The arithmetic crystal class is denoted by a modification of the symbol of the three-dimensional symmorphic space group of this class (see Chapter 1.4 ) plus an indication for the row matrix σ (having entries ). In this way, one obtains the so-called one-line symbols used in Tables 9.8.3.1 and 9.8.3.2.
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As an example, the symbol denotes a Bravais class for which the main reflections belong to a B-centred monoclinic lattice (unique axis c) and the satellite positions are generated by the point-group transforms of . Then the matrix σ becomes . It has as irrational part and as rational part . The external part of the (3 + 1)-dimensional point group of the Bravais lattice is 2/m. By use of the relation [cf. (9.8.2.4)] we see that the operations 2 and m are associated with the internal space transformations ɛ = 1 and ɛ = −1, respectively. This is denoted by the one-line symbol for the (3 + 1)-dimensional point group of the Bravais lattice. In direct space, the symmetry operation {R, ɛ(R)} is represented by the matrix Γ(R) which transforms the components , of a vector to: The operations (2, 1) and are represented by the matrices: The 3 × 3 part of each matrix is obtained by considering the action of R on the external part v of . The 1 × 1 part is the value of the ɛ associated with R and the remaining part follows from the relation
Bravais classes can be denoted in an alternative way by two-line symbols. In the two-line symbol, the Bravais class is given by specifying the arithmetic crystal class of the external symmetry by the symbol of its symmorphic space group, the associated elements by putting their symbol under the corresponding symbols of , and by the rational part indicated by a prefix. In the following table, this prefix is given for the components of that play a role in the classification. Note that the integers appearing here are not equivalent to zero because they express components with respect to a conventional lattice basis (and not a primitive one). For the Bravais class mentioned above, the two-line symbol is . This symbol has the advantage that the internal transformation (the value of ɛ) is explicitly given for the corresponding generators. It has, however, certain typographical drawbacks. It is rare for the printer to put the symbol together in the correct manner: .
In Tables 9.8.3.1 and 9.8.3.2 the symbols for the (2 + d)- and (3 + 1)-dimensional Bravais classes are given in the one-line form. It is, however, easy to derive from each one-line symbol the corresponding two-line symbol because the bottom line for the two-line symbol appears in the tables as the internal part of the point-group symbol.
The number of symbols in the bottom line of the two-line symbol should be equal to that of the generators given in the top line. A symbol `1' is used in the bottom line if the corresponding is the unit transformation. If necessary, a mirror perpendicular to a crystal axis is indicated by and one that is not by . This situation only occurs for . So the (2 + 2)-dimensional class is actually and is different from the class . In a one-line symbol, their difference is apparent, the first being 4mp(α0), whereas the second is 4mp(αα).
In Table 9.8.3.3, the geometric and the arithmetic crystal classes of (3 + 1)-dimensional superspace are given.
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The symbols for geometric crystal classes indicate the pairs of the generators of the point group. This is done by giving the crystal class for the point group and the symbols for the corresponding elements of . So, for example, the geometric crystal class belonging to the holohedral point group of the Bravais class , mentioned above, is .
The notation for the arithmetic crystal classes is similar to that for the Bravais classes. In the tables, their one-line symbols are given. They consist of the (modified) symbol of the three-dimensional symmorphic space group and, in parentheses, the appropriate components of the modulation wavevector. The three arithmetic crystal classes implying a lattice belonging to the Bravais class are , , and . The corresponding geometric crystal classes are , , and .
The transformations belonging to a (3 + 1)-dimensional superspace group consist of a point-group transformation given by the integral matrix Γ(R) and of the associated translation. So the superspace group is determined by the arithmetic crystal class of its point group and the corresponding translational components. The symbol for the arithmetic crystal class has been discussed in Subsection 9.8.3.2. Given a point-group transformation , the associated translation is determined up to a lattice translation. As in three dimensions, the translational part generally depends on the choice of origin. To avoid this arbitrariness, one decomposes that translation into a component (called intrinsic) independent of the origin, and a remainder. The (3 + 1)-dimensional translation associated with the point-group transformation is given by Its origin-invariant part is given by where n is now the order of the point-group transformation R so that is the identity. As customary also in three-dimensional crystallography, one indicates in the space-group symbol the invariant components . Notice that this means that there is an origin for in (3 + 1)-dimensional superspace such that the translation associated with has these components. This origin, however, may not be the same for different transformations , as is known in three-dimensional crystallography.
Written in components, the non-primitive translation associated with the point-group element is , where can be written as . In accordance with (9.8.1.12), δ is defined as . The origin-invariant part of is where The internal transformation = ɛ(R) = ɛ is either +1 or −1. When ɛ = −1 it follows from (9.8.3.6) that . For , one has . Because in that case it follows that
For of order n, is the identity and the associated translation is a lattice translation. The ensuing values for τ are or (modulo integers). This remains true also in the case of a centred basis. The symbol of the (3 + 1)-dimensional space-group element is determined by the invariant part of its three-dimensional translation and τ. Again, that information can be given in terms of either a one-line or a two-line symbol.
In the one-line symbol, one finds: the symbol according to International Tables for Crystallography, Volume A, for the space group generated by the elements {R|v}, in parentheses the components of the modulation vector q followed by the values of τ, one for each generator appearing in the three-dimensional space-group symbol. A letter symbolizes the value of τ according to As an example, consider the superspace group The external components of the elements of this group form the three-dimensional space group . The modulation wavevector is αa* + βb* with respect to a conventional basis of the monoclinic lattice with unique axis c. Therefore, the point group is . The point-group element has associated a non-primitive translation with invariant part and the point-group generator (m, 1) one with .
In the two-line symbol, one finds in the upper line the symbol for the three-dimensional space group, in the bottom line the value of τ for the case ɛ = +1 and the symbol `' when ɛ = −1. The rational part of q is indicated by means of the appropriate prefix. In the case considered, qr = 000. So the prefix is P and the same superspace group is denoted in a two-line symbol as In Table 9.8.3.5, the (3 + 1)-dimensional space groups are given by one-line symbols. These are so-called short symbols. Sometimes, a full symbol is required. Then, for the example given above one has and , respectively. Note that in the short one-line symbol for τ = 0 superspace groups (where the non-primitive translations can be transformed to zero by a choice of the origin) the zeros for the translational part are omitted. Not so, of course, in the full symbol. For example, short symbol P21/m(αβ0) and full symbol P1121/m(αβ0)0000. Table 9.8.3.5 is an adapted version of the tables given by de Wolff, Janssen & Janner (1981) and corrected by Yamamoto, Janssen, Janner & de Wolff (1985).
The indexing of diffraction vectors is a matter of choice of basis. When the basis chosen is not a primitive one, the indices have to satisfy certain conditions known as centring conditions. This holds for the main reflections (centring in ordinary space) as well as for satellites (centring in superspace). These centring conditions for reflections have been discussed in Subsection 9.8.2.1.
In addition to these general reflection conditions, there may be special reflection conditions related to the existence of non-primitive translations in the (3 + 1)-dimensional space group, just as is the case for glide planes and screw axes in three dimensions.
Special reflection conditions can be derived from transformation properties of the structure factor under symmetry operations. Transforming the geometric structure factor by an element , one obtains Therefore, if RH = H, the corresponding structure factor vanishes unless is an integer.
The form of such a reflection condition in terms of allowed or forbidden sets of indices depends on the basis chosen. When a lattice basis is chosen, one has Then the reflection condition becomes
In terms of external and internal shift components, the reflection condition can be written as With and , (9.8.3.14) gives For and , (9.8.3.15) takes the form (9.8.3.13): When the modulation wavevector has a rational part, one can choose another basis (Subsection 9.8.2.1) such that K′ = K + mqr has integer coefficients: Then, (9.8.3.15) with becomes and (9.8.3.16) transforms into in which , and are the components of v with respect to the basis , and .
As an example, consider a (3 + 1)-dimensional space-group transformation with R a mirror perpendicular to the x axis, , and with b orthogonal to a. The modulation wavevector is supposed to be . Then . The vectors H left invariant by R satisfy the relation 2h + m = 0. For such a vector, the reflection condition becomes For the basis , , c*, the rational part of the wavevector vanishes. The indices with respect to this basis are H = h + k + m, K = h − k, L = l and m. The condition now becomes Of course, both calculations give the same result: k + m = 2n for h, k, l, −2h and H − K + m = 4n for H, −H, L, m.
The special reflection conditions for the elements occurring in (3 + 1)-dimensional space groups are given in Table 9.8.3.5.
In the tables, Bravais classes, point groups, and space groups are given for three-dimensional incommensurate modulated crystals with a modulation of dimension one and for two-dimensional crystals (e.g. surfaces) with one- and two-dimensional modulation (Janssen, Janner & de Wolff, 1980). In the following, we discuss briefly the information given. Examples of their use can be found in Subsection 9.8.3.5.
To determine the symmetry of the modulated phase, one first determines its average structure, which is obtained from the main reflections. Since this structure has three-dimensional space-group symmetry, this analysis is performed in the usual way.
The diffraction pattern of the three-dimensional modulated phase can be indexed by 3 + 1 integers. The Bravais class is determined by the symmetry of the vector module spanned by the 3 + 1 basis vectors. The crystallographic system of the pattern is equal to or lower than that implied by the main reflections. One chooses a conventional basis (qr = 0) for the vector module, and finds the Bravais class from the general reflection conditions using Table 9.8.3.6. The relation between indices hklm with respect to the basis a*, b*, c*, and q and HKLm with respect to the conventional basis , , , and is also given there.
Table 9.8.3.2(a) gives the number labelling the (3 + 1)-dimensional Bravais class, its symbol, its external and internal point group, and the modulation wavevector. Moreover, the superspace conventional basis (for which the rational part qr vanishes) and the corresponding (3 + 1)-dimensional centring are given. Because the four-dimensional lattices belong to Euclidean Bravais classes, the corresponding class is also given in the notation of Janssen (1969) and Brown et al. (1978).
The point group of the modulated structure is a subgroup of the holohedry of its lattice Λ. In Table 9.8.3.3, for each system the (3 + 1)-dimensional point groups are given. Each system contains one or more Bravais classes. Each geometric crystal class contains one or more arithmetic crystal classes. The (3 + 1)-dimensional arithmetic classes belonging to a given geometric crystal class are also listed in Table 9.8.3.3.
Starting from the space group of the average structure, one can determine the (3 + 1)-dimensional superspace group. In Table 9.8.3.5, the full list of these (3 + 1)-dimensional superspace groups is given for the incommensurate case and are ordered according to their basic space group. They have a number n.m where n is the number of the basic space group one finds in International Tables for Crystallography, Volume A. The various (3 + 1)-dimensional superspace groups for each basic group are distinguished by the number m. Furthermore, the symbol of the basic space group, the point group, and the symbol for the corresponding superspace group are given. In the last column, the special reflection conditions are listed for typical symmetry elements. These may help in the structure analysis. The (2 + d)-dimensional superspace groups, relevant for modulated surface structures, are given in Table 9.8.3.4.
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(A) Na2CO3
Na2CO3 has a phase transition at about 753 K from the hexagonal to the monoclinic phase. At about 633 K, one vibration mode becomes unstable and below the transition temperature Ti = 633 K there is a modulated γ-phase (de Wolff & Tuinstra, 1986). At low temperature (128 K), a transition to a commensurate phase has been reported.
The main reflections in the modulated phase belong to a monoclinic lattice, and the satellites to a modulation with wavevector q = αa* + γc*, b axis unique. The dimension of the modulation is one. The main reflections satisfy the condition Therefore, the lattice of the average structure is C-centred monoclinic. For the satellites, the same general condition holds (hklm, h + k = even). From Table 9.8.3.6, one sees after a change of axes that the Bravais class of the modulated structure is Table 9.8.3.2(a) shows that the point group of the vector module is . The point group of the modulated structure is equal to or a subgroup of this one.
The space group of the average structure determined from the main reflections is C2/m (No. 12 in International Tables for Crystallography, Volume A). The superspace group may then be determined from the special reflection condition using Table 9.8.3.5. There are five superspace groups with basic group No. 12. Among them there are two in Bravais class 4. The reflection condition mentioned leads to the group In principle, the superspace group could be a subgroup of this, but, since the transition normal–incommensurate is of second order, Landau theory predicts that the basic space group is the symmetry group of the unmodulated monoclinic phase, which is .
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(B) ThBr4
Thorium tetrabromide has an incommensurately modulated phase below = 95 K (Currat, Bernard & Delamoye, 1986). Above that temperature, the structure has space group (No. 141 in International Tables for Crystallography, Volume A). At , a mode becomes unstable and a modulated β-phase sets in with modulation wavevector γc*. The dimension of the modulation is one, consequently.
The main reflections belong to a tetragonal lattice. The general reflection condition is Looking at Table 9.8.3.6, one finds the Bravais class to be No. 21 = I4/mmm(00γ). Table 9.8.3.2(a) gives for the point group of the vector module.
For the determination of the symmetry group of the modulated structure, one has the special reflection conditions Higher-order satellites have not been observed. The main reflections lead to the basic group . If one generalizes the reflection condition observed for 0klm to 0klm, m = even, the superspace group is found from Table 9.8.3.5 under the groups 141.x as
(C) PAMC
Bis(n-propylammonium) tetrachloromanganate (PAMC) has several phase transitions. Above about 395 K, it is orthorhombic with space group Abma. At , this β-phase goes over into the incommensurately modulated γ-phase (Depmeier, 1986; Kind & Muralt, 1986). The wavevector of the modulation is . Therefore, the dimension of the modulation is one. Interchanging the a and c axes, one sees from Table 9.8.3.2(a) that the Bravais class is No. 14 = mmmC(10γ). In this new setting, the conventional basis of the vector module is a*, b*, c*, and γc* and the general reflection condition becomes Therefore, if one considers the vector module as the projection of a four-dimensional lattice, the reflection condition corresponds to a centring in four dimensions.
The point group of the vector module is . The basic space group being Abma (or Ccmb in the new setting), the superspace group follows from Table 9.8.3.5 as or, in the original setting No. 64.4 can be excluded because the reflections do not show the special reflection condition 0KLm, m = even.
The invariant part of the translation part of a (3 + 1)-dimensional superspace-group element is uniquely determined by (9.8.3.5). This does not imply that for each element of the point group there is a translation for which the invariant part is unique up to lattice vectors. The reason is that, for a given element R of the point group and given origin, may be changed when R is combined with a three-dimensional lattice translation . This situation is well known in ordinary three-dimensional crystallography. For example, the twofold rotation in the space group has according to Volume A of International Tables for Crystallography a translation part . Its invariant part is . However, when the translation part is equivalently taken as , the invariant part vanishes. Therefore, in the symbol for that space group, the corresponding generator is given as the rotation `2' and not as the screw axis `'.
The same situation may occur in 3 + 1 dimensions. This can be seen very clearly from the definition of τ [equation (9.8.3.8)]. Since v is only determined modulo a lattice vector, one may add to it a lattice vector that has a non-vanishing product with qr. This results in a change for τ. For example, the (3 + 1)-dimensional space group has a mirror perpendicular to the a axis with associated value τ = 0. The parallel mirror at a distance a/2 has v = a and consequently . Hence, the symbols and indicate the same group. This non-uniqueness in the symbol, however, does not have serious practical consequences.
Another source of ambiguity is the fact that the assignment of a satellite to a main reflection is not unique. For example, the reflection conditions for the group are h + k + l = even because of the centring and l + m = even and h + m = even for h0lm because of the two glide planes perpendicular to the b axis. When one takes for the modulation vector q = γ′c* = (1 − γ)c*, the new indices are h, k, l′, and m′ with l′ = l + m and m′ = −m. Then the reflection conditions become l′ = even and h + m = even for . The first of these conditions implies the symbol for the group considered. This, however, is the symbol for the nonequivalent group with condition h = even for h0lm. This difficulty may be avoided by sometimes using a non-standard setting of the three-dimensional space group (see Yamamoto et al., 1985). In this case, the setting I2ab instead of I2cb avoids the problem.
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