Symmetry operations, group inverse

Mathematics (Hassel, 1830) has shown that there are only 32 combinations of symmetry operations (rotation, inversion, and reflection) that are consistent with a three-dimensional crystal lattice. These 32 point groups, or crystal classes, can be grouped into one of the seven crystal systems given in Table 2.1. There are four types of crystal lattices primitive (P), end-centered (C, B, and A), face-centered (/O, and body-centered (/). The primitive lattice contains a lattice point at each comer of the unit cell, the end-centered lattice has an additional lattice point on one of the lattice faces, the face-centered lattice has an extra lattice on each of the lattice faces, and the body-centered lattice has an extra lattice point at the center of the crystal lattice. By combining the seven crystal systems with the four lattice types (P, C, I, F), 14 unique crystal lattices, also known as Bravais lattices (Bravais, 1849), are produced. 

Table 6-1. C2(l molecular poinl group. The electronic stales of the flat T6 molecule are classified according lo the lwo-1 old screw axis (C2). inversion (/). and glide plane reflection (o ) symmetry operations. The A and lt excited slates transform like translations Oi along the molecular axes and are optically allowed. The Ag and Bg stales arc isoniorphous with the polarizability tensor components (u), being therefore one-photon forbidden and Iwo-pholon allowed.

The group-subgroup relation of the symmetry reduction from diamond to zinc blende is shown in Fig. 18.3. Some comments concerning the terminology have been included. In both structures the atoms have identical coordinates and site symmetries. The unit cell of diamond contains eight C atoms in symmetry-equivalent positions (Wyckoff position 8a). With the symmetry reduction the atomic positions split to two independent positions (4a and 4c) which are occupied in zinc blende by zinc and sulfur atoms. The space groups are translationengleiche the dimensions of the unit cells correspond to each other. The index of the symmetry reduction is 2 exactly half of all symmetry operations is lost. This includes the inversion centers which in diamond are present in the centers of the C-C bonds. 

It is noted that two successive symmetry transformations of a system leave that system invariant. The product of the two operations is therefore also a symmetry operation of the system. The set of symmetry transformations is therefore closed under the law of successive transformations. An identity transformation that leaves the system unchanged clearly belongs to the set. It is not difficult to see that any given symmetry transformation has an inverse that also belongs to the set. Since successive transformations of the set obey the associative law it finally follows that the set constitutes a group. 

The unit cell considered here is a primitive (P) unit cell that is, each unit cell has one lattice point. Nonprimitive cells contain two or more lattice points per unit cell. If the unit cell is centered in the (010) planes, this cell becomes a B unit cell for the (100) planes, an A cell for the (001) planes a C cell. Body-centered unit cells are designated I, and face-centered cells are called F. Regular packing of molecules into a crystal lattice often leads to symmetry relationships between the molecules. Common symmetry operations are two- or three-fold screw (rotation) axes, mirror planes, inversion centers (centers of symmetry), and rotation followed by inversion. There are 230 different ways to combine allowed symmetry operations in a crystal leading to 230 space groups.12 Not all of these are allowed for protein crystals because of amino acid asymmetry (only L-amino acids are found in proteins). Only those space groups without symmetry (triclinic) or with rotation or screw axes are allowed. However, mirror lines and inversion centers may occur in protein structures along an axis. 

When two symmetry operations are combined, a third symmetry operation can result automatically. For example, the combination of a twofold rotation with a reflection at a plane perpendicular to the rotation axis automatically results in an inversion center at the site where the axis crosses the plane. It makes no difference which two of the three symmetry operations are combined (2, m or T), the third one always results (Fig. 3.6). Hermann-Mauguin Point-group Symbols... 

For centrosymmetric systems with a centre of inversion /, subscripts g (symmetric) and u (antisymmetric) are also used to designate the behaviour with respect to the operation of inversion. The molecule trans-butadiene belongs to the point group Cik (Figure 2.13b). Under this point group the symmetry operations are /, C2Z, and i, and the following symmetry species can be generated ... 

But this does nob end the tale of possible arrangements. Hitherto we have considered only those symmetry operations which carry us from one atom in the crystal to another associated with the same lattice point—the symmetry operations (rotation, reflection, or inversion through a point) which by continued repetition always bring us back to the atom from which we started. These are the point-group symmetries which were already familiar to us in crystal shapes. Now in "many space-patterns two additional types of symmetry operations can be discerned--types which involve translation and therefore do not occur in point-groups or crystal shapes. 

Since inversion commutes with every other symmetry operation (this will be proved in Section 9.3), point groups of molecules with a center of symmetry have / in a class by itself. 

The final requirement, that every element of the group have an inverse, is also satisfied. For a group composed of symmetry operations, we may define the inverse of a given operation as that second operation, which will exactly undo what the given operation does. In more sophisticated terms, the reciprocal S of an operation R must be such that RS = SR = E. Let us consider each type of symmetry operation. For <7, reflection in a plane, the inverse is clearly a itself a x a = cr = E. For proper rotation, C , the inverse is C" m, for C x C "m = C" = E. For improper rotation, S , the reciprocal depends on whether m and n are even or odd, but a reciprocal exists in each of the four possible cases. When n is even, the reciprocal of S% is S m whether m is even or odd. When n is odd and m is even, S% — C , the reciprocal of which is Q m. For S" with both n and m odd we may write 5 = C a. The reciprocal would be the product Q ma, which is equal to and which... 

Symmetry Notation.—A state is described in terms of the behavior of the electronic wave function under the symmetry operations of the point group to which the molecule belongs. The characters of the one-electron orbitals are determined by inspection of the character table the product of the characters of the singly occupied orbitals gives the character of the molecular wave function. A superscript is added on the left side of the principal symbol to show the multiplicity of the state. Where appropriate, the subscript letters g (gerade) and u (ungerade) are added to the symbol to show whether or not the molecular wave function is symmetric with respect to inversion through a center of symmetry. 

The complete set of point symmetry operators that is generated from the operators Ri R2... that are associated with the symmetry elements (as shown, for example, in Table 2.2) by forming all possible products like R, Ry and including E, satisfies the necessary group properties the set is complete (satisfies closure), it contains E, associativity is satisfied, and each element (symmetry operator) has an inverse. That this is so may be verified in any particular case we shall see an example presently. Such groups of point symmetry operators are called point groups. For example, if a system has an S4 axis and no... 

These rules show that the G<- G transition, in contrast with the others, is purely rotational. In the coordinate system shown in Figure 8.20, the transition states for the cis and trans paths of interconversion have symmetry axes and C2y and relate to the symmetry groups and C2h, respectively. The different symmetries of the transition states results from the fact that the same permutation relates to different symmetry operations in C2v and C2h. For example, (ab)(14)(28)(36) is equivalent to inversion in C2h, while in it corresponds to the reflection in the axy plane. The symmetry of the reaction path does not affect the symmetry of states with even Ka (and Ka = 0). However, the selection rules for transitions Ka = 1 0 are different for cis and trans paths. The classifica-... 

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