Crystal translational symmetry

When a defect is introduced into a crystalline environment, crystal translational symmetry can no longer be invoked to transform the problem into tractable form as is done in band-structure calculations. Most of the computational treatments of defects in semiconductors rely on approximations to the defect environment that fall into one of three categories cluster, supercell (or cyclic cluster), and Green s function. 

Clearly, these giant clusters are going to be a difficult problem if treated in the manner of small, molecular clusters. But if we can t handle the [A Ris]3- cluster, you ask, what approach can we use to understand that of bulk Al The molecular perspective we have taken thus far makes the problem look far worse. With 1023 Al atoms don t we need to consider 3 x 1023 valence electrons and 4 x 1023 atomic functions for the simplest MO treatment Well, yes, but fortunately for substances in the form of single crystals translational symmetry provides a straightforward way around the problem. It is presented in the next section. 

In a lattice of the type shown in Figure 6.1 (where a two-dimensional lattice is shown), each point consists of an atom, an atomic ion, a molecule, or a molecular ion. It is possible to move one step in all crystal directions and get back the (infinite) crystal (translational symmetry). It is required from the unit cell that (1) translational symmetry is still valid, (2) all unit cells together fill the volume of the crystal, and (3) different unit cells do not overlap. Despite these requirements, a unit cell is not unique, since the crystal axes are not unique, but can be defined in more than one way. The lengths of the unit cell axes are called the lattice constants. 

Order and dense packing are relative in tire context of tliese systems and depend on tire point of view. Usually tire tenn order is used in connection witli translational symmetry in molecular stmctures, i.e. in a two-dimensional monolayer witli a crystal stmcture. Dense packing in organic layers is connected witli tire density of crystalline polyetliylene. 

A. Pullet, J.-P. Matie Vibration spectra and symmetry of crystals (translation in to Russian) Mir, Moscow, 1974. 

Symmetry properties which have so far been successfully treated by the projection operator method, include translational symmetry in crystals, cyclic systems, spin, orbital and total angular momenta, and further applications are in progress. ... 

With the chemical structure of PbTX-1 finally known and coordinates for the molecule available from the dimethyl acetal structure, we wanted to return to the natural product crystal structure. From the similarities in unit cells, we assumed that the structures were nearly isomorphous. Structures that are isomorphous are crystallographically similar in all respects, except where they differ chemically. The difference between the derivative structure in space group C2 and the natural product structure in P2. (a subgroup of C2) was that the C-centering translational symmetry was obeyed by most, but not all atoms in the natural product crystal. We proceeded from the beginning with direct methods, using the known orientation of the PbTX-1 dimethyl acetal skeleton (assuming isomorphism) to estimate phase... 

The number density matrix for a crystal with translation symmetry can be written in terms of its natural orbitals [23, 24], as... 

Strictly speaking, a symmetry-translation is only possible for an infinitely extended object. An ideal crystal is infinitely large and has translational symmetry in three dimensions. To characterize its translational symmetry, three non-coplanar translation vectors a, b and c are required. A real crystal can be regarded as a finite section of an ideal crystal this is an excellent way to describe the actual conditions. 

Translational symmetry is the most important symmetry property of a crystal. In the Hermann-Mauguin symbols the three-dimensional translational symmetry is expressed by a capital letter which also allows the distinction of primitive and centered crystal lattices (cf. Fig. 2.6, p. 8) ... 

Screw rotation. The symmetry element is a screw axis. It can only occur if there is translational symmetry in the direction of the axis. The screw rotation results when a rotation of 360/1V degrees is coupled with a displacement parallel to the axis. The Hermann-Mauguin symbol is NM ( N sub M )-,N expresses the rotational component and the fraction M/N is the displacement component as a fraction of the translation vector. Some screw axes are right or left-handed. Screw axes that can occur in crystals are shown in Fig. 3.4. Single polymer molecules can also have non-crystallographic screw axes, e.g. 103 in polymeric sulfur. 

Normally, solids are crystalline, i.e. they have a three-dimensional periodic order with three-dimensional translational symmetry. However, this is not always so. Aperiodic crystals do have a long-distance order, but no three-dimensional translational symmetry. In a formal (mathematical) way, they can be treated with lattices having translational symmetry in four- or five-dimensional space , the so-called superspace their symmetry corresponds to a four- or five-dimensional superspace group. The additional dimensions are not dimensions in real space, but have to be taken in a similar way to the fourth dimension in space-time. In space-time the position of an object is specified by its spatial coordinates x, y, z the coordinate of the fourth dimension is the time at which the object is located at the site x, y, z. 

Several kinds of intermediate states exist between the state of highest order in a crystal having translational symmetry in three dimensions and the disordered distribution of particles in a liquid. Liquid crystals are closest to the liquid state. They behave macroscopically like liquids, their molecules are in constant motion, but to a certain degree there exists a crystal-like order. 

Plastic crystals and crystals with orientational disorder still fulfill the three-dimensional translational symmetry, provided a mean partial occupation is assumed for the atomic positions of the molecules whose orientations differ from unit cell to unit cell ( split positions ). 

Among crystals with stacking faults the lack of a periodic order is restricted to one dimension this is called a one-dimensional disorder. If only a few layer positions occur and all of them are projected into one layer, we obtain an averaged structure. Its symmetry can be described with a space group, albeit with partially occupied atomic positions. The real symmetry is restricted to the symmetry of an individual layer. The layer is a three-dimensional object, but it only has translational symmetry in two dimensions. Its symmetry is that of a layer group there exist 80 layer-group types. 

In the above relation, quantum states of phonons are characterized by the surface-parallel wave vector kg, whereas the rest of quantum numbers are indicated by a the latter account for the polarization of a quasi-particle and its motion in the surface-normal direction, and also implicitly reflect the arrangement of atoms in the crystal unit cell. A convenient representation like this allows us to immediately take advantage of the translational symmetry of the system in the surface-parallel direction so as to define an arbitrary Cartesian projection (onto the a axis) for the... 

Because of translational symmetry special directions occur in crystals and it often happens that the electric fields associated with light rays transmitted through a crystal are channeled to vibrate in a special direction that provides an easy passage. This means that the light becomes polarized. 

In a perfect crystal at 0 K all atoms are ordered in a regular uniform way and the translational symmetry is therefore perfect. The entropy is thus zero. In order to become perfectly crystalline at absolute zero, the system in question must be able to explore its entire phase space the system must be in internal thermodynamic equilibrium. Thus the third law of thermodynamics does not apply to substances that are not in internal thermodynamic equilibrium, such as glasses and glassy crystals. Such non-ergodic states do have a finite entropy at the absolute zero, called zero-point entropy or residual entropy at 0 K. 

So far, the solids that we have studied have been ordered, in the sense that they possess perfect translational symmetry. However, this perfection is really an idealization and, in reality, an actual crystal can be expected to have some sort of disorder, which breaks the long-range periodicity of the lattice. There are a number of ways in which disorder can arise. For instance, interstitial disorder occurs when an impurity atom is placed in the vacant space between two substrate atoms, which remain at their original locations in the lattice. Another situation is that of structural disorder, where the substrate atoms move away from their positions on the perfect lattice. However, the situation of interest in this chapter is that of substitutional disorder. Here, a perfect lattice of one type of atoms (say, A) has some of its members randomly replaced by another type (B). The result is a structurally periodic lattice, but with the constituent atoms A and B randomly placed on the lattice sites. The relative numbers of A and B atoms can be represented by the concentrations ca and cB, with ca + cB = l. The randomness of this type of solid introduces a level of difficulty into the theory, that we have not yet encountered. 

Molecules, in general, have some nontrivial symmetry which simplifies mathematical analysis of the vibrational spectrum. Even when this is not the case, the number of atoms is often sufficiently small that brute force numerical solution using a digital computer provides the information wanted. Of course, crystals have translational symmetry between unit cells, and other elements of symmetry within a unit cell. For such a periodic structure the Hamiltonian matrix has a recurrent pattern, so the problem of calculating its eigenvectors and eigenvalues can be reduced to one associated with a much smaller matrix (i.e. much smaller than 3N X 3N where N is the number of atoms in the crystal). 

A technical problem occurs when one attempts to apply this approach to study a surface. The calculations described for the bulk crystal assume perfect symmetry and a solid of infinite extent often described in terms of cyclic or periodic boundary conditions. However, for a surface, the translational symmetry is broken, and the usual expansions in Fourier series used for the bulk are not appropriate. For the bulk, a few atoms form a basis which is attached to a lattice cell, and this cell is... 

This section deals with the dynamics of collective surface vibrational excitations, i.e. with surface phonons. A surface phonon is defined as a localized vibrational excitation of a semi-infinite crystal, with an amplitude which has wavelike characteristics parallel to the surface and decays exponentially into the bulk, perpendicular to the surface. This behavior is directly linked to the broken translational invariance at a surface, the translational symmetry being confined here to the directions parallel to the surface. 

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