Symmetry operations, group proper

Here /, are the three moments of inertia. The symmetry index a is the order of the rotational subgroup in the molecular point group (i.e. the number of proper symmetry operations), for H2O it is 2, for NH3 it is 3, for benzene it is 12 etc. The rotational partition function requires only information about the atomic masses and positions (eq. (12.14)), i.e. the molecular geometry. 

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... 

Then Q +IR Q is a point group P which is isomorphous with P and therefore has the same class structure as P. The isomorphism follows from the fact that I commutes with any proper or improper rotation and therefore with any other symmetry operator. Multiplication tables for P and P are shown in Table 2.7 we note that these have the same structure and that the two groups have corresponding classes, the only difference being that some products Xare replaced by IXin P. Examples are given below. 

The space group G of a crystal is the set of all symmetry operators that leave the appearance of the crystal pattern unchanged from what it was before the operation. The most general kind of space-group operator (called a Seitz operator) consists of a point operator R (that is, a proper or improper rotation that leaves at least one point invariant) followed by a translation v. For historical reasons the Seitz operator is usually written R v. However, we shall write it as (R ) to simplify the notation for sets of space-group operators. When a space-group operator acts on a position vector r, the vector is transformed into... 

We are not going to review here the transformation properties of spatial wave functions under the symmetry operations of molecular point groups. To prepare the discussion of the transformation properties of spinors, we shall put some effort, however, in discussing the symmetry operations of 0(3)+, the group of proper rotations in 3D coordinate space (i.e., orthogonal transformations with determinant + 1). Reflections and improper rotations (orthogonal transformations with determinant -1) will be dealt with later. 

It has to be noted that the relation between the elements of 0(3)+ (also called SO(3), the group representing proper rotations in 3D coordinate space) and SU(2) (the special unitary group in two dimensions) is not a one-to-one correspondence. Rather, each R matches two matrices u. Molecular point groups including symmetry operations for spinors therefore exhibit two times as many elements as ordinary point groups and are dubbed double groups. 

The operators of discrete rotational groups, best described in terms of both proper and improper symmetry axes, have the special property that they leave one point in space unmoved hence the term point group. Proper rotations, like translation, do not affect the internal symmetry of an asymmetric motif on which they operate and are referred to as operators of the first kind. The three-dimensional operators of improper rotation are often subdivided into inversion axes, mirror planes and centres of symmetry. These operators of the second kind have the distinctive property of inverting the handedness of an asymmetric unit. This means that the equivalent units of the resulting composite object, called left and right, cannot be brought into coincidence by symmetry operations of the first kind. This inherent handedness is called chirality. 

The elements in a group can be characterized by their periods. In this context the period of an element is the minimum number of times it must be multiplied by itself before the identity E is obtained. In the case of symmetry operations (Table 1) the period of the identity operation E is, of course, 1 the periods of the reflections a are always 2 the periods of the proper rotations C are the periods of the even improper rotations Sm are 2 and the periods of the odd improper rotations Sm+x are 4n + 2. 

Does the object has an even-order improper rotation axis S2 but no planes of symmetry or any proper rotation axis other than one collinear with the improper rotation axis The presence of an improper rotation axis of even order S2 without any noncollinear proper rotation axes or any reflection planes indicates the symmetry point group S2 with 2n operations. 

The high-symmetry point groups Ik, Of, and 7 are well known in chemistry and are represented by such classic molecules as C6o Sp6, and CH4. For each of these point groups, there is also a purely rotational subgroup (/, O, and T, respectively) in which the only symmetry operations other than the identity operation are proper axes of rotation. The symmetry operations for these point groups are in Table 4-5. 

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