Symmetry operations improper rotation

Identity element, 387-388 Identity operation, 54, 395 Improper axis of symmetry, 53 Improper rotation, 396 Index of refraction, 132 INDO method, 71, 75-76 and ESR coupling constants, 380 and force constants, 245 and ionization potentials, 318 and NMR coupling constants, 360 Induced dipole moment, 187 Inertial defect, 224-225 Inertia tensor, 201... 

A symmetry operation is a transformation of a system that leaves an object in an indistinguishable position. For molecular systems, we need be concerned with only two types of symmetry operations proper rotations (C ) and improper rotations (S ). A C is a rotation around an axis by (360/ )° that has the net effect of leaving the position of the object unchanged. Thus, a C2 is a 180° rotation, a C3 a 120° rotation, and so on. These are termed "proper" rotations, because it is actually physically possible to rotate an object by 180° or 120°. Some examples are shown below, with the atoms labeled only to highlight the operation. 

Define the following terms symmetry operation, symmetry element, principal axis, identity operation, improper rotation, inversion, symmetry group, point group, conjugate elements, similarity transformation and class. 

An electric dipole operator, of importance in electronic (visible and uv) and in vibrational spectroscopy (infrared) has the same symmetry properties as Ta. Magnetic dipoles, of importance in rotational (microwave), nmr (radio frequency) and epr (microwave) spectroscopies, have an operator with symmetry properties of Ra. Raman (visible) spectra relate to polarizability and the operator has the same symmetry properties as terms such as x2, xy, etc. In the study of optically active species, that cause helical movement of charge density, the important symmetry property of a helix to note, is that it corresponds to simultaneous translation and rotation. Optically active molecules must therefore have a symmetry such that Ta and Ra (a = x, y, z) transform as the same i.r. It only occurs for molecules with an alternating or improper rotation axis, Sn. 

As an example, which will also lead us to the concept of qualitative completeness, consider the allene skeleton, as shown in Fig. 8, and for the moment consider only achiral ligands. Besides the unit element, the symmetry group of the skeleton, "Dm, consists of the rotation operations (in permutation group notation) (12)(34), (13)(24), and (14)(23), plus the improper rotations (1)(2)(34), (12)(3)(4), (1324), and (1432). 

For each symmetry element of the second kind (planes of reflection and improper axes of rotation) one counts according to Eq. (1) the pairs of distinguishable ligands at ligand sites which are superimposable by symmetry operations of the second kind. 

If rotation about an axis by 360°ln followed by reflexion through a plane perpendicular to the axis produces an equivalent configuration of a molecule, then the molecule contains an improper axis of symmetry. Such an axis is denoted by Sn, the associated symmetry operation having been described in the previous sentence. The C3 axis of the PC15 molecule is also an S3 axis. The operation of S3 on PC15 causes the apical (i.e. out-of-plane) chlorine atoms to exchange places. 

Improper rotation axis. Rotation about an improper axis is analogous to rotation about a proper synunetry axis, except that upon completion of the rotation operation, the molecule is mirror reflected through a symmetry plane perpendicular to the improper rotation axis. These axes and their associated rotation/reflection operations are usually abbreviated X , where n is the order of the axis as defined above for proper rotational axes. Note that an axis is equivalent to a a plane of symmetry, since the initial rotation operation simply returns every atom to its original location. Note also that the presence of an X2 axis (or indeed any X axis of even order n) implies that for every atom at a position (x,y,z) that is not the origin, there will be an identical atom at position (—x,—y,—z) the origin in such a system is called a point of inversion , since one may regard every atom as having an identical... 

This is the operation of clockwise rotation by 2w/ about an axis followed by reflection in a plane perpendicular to that axis (or vice versa, the order is not important). If this brings the molecule into coincidence with itself, the molecule is said to have a n-fold alternating axis of symmetry (or improper axis, or rotation-reflection axis) as a symmetry element. It is the knight s move of symmetry. It is symbolized by Sn and illustrated for a tetrahedral molecule in Fig. 2-3.3.f... 

Our convention is that a symmetry operation R changes the locations of points in space, while the coordinate axes remain fixed. In contrast in Section 1.2 we considered a change (proper or improper rotation) of coordinate axes, while, the points in space remained fixed Let x y z be a set of axes derived from the xyz axes by a proper or improper rotation. Consider a point fixed in space. We found that its coordinates in the x y z system are related to its coordinates in the xyz system by (1.120) or (2.29) ... 

We consider four kinds of symmetry elements. For an n fold proper rotation axis of symmetry Cn, rotation by 2n f n radians about the axis is a symmetry operation. For a plane of symmetry a, reflection through the plane is a symmetry operation. For a center of symmetry /, inversion through this center point is a symmetry operation. For an n-fold improper rotation axis Sn, rotation by lir/n radians about the axis followed by reflection in a plane perpendicular to the axis is a symmetry operation. To denote symmetry operations, we add a circumflex to the symbol for the corresponding symmetry element. Thus Cn is a rotation by lit/n radians. Note that since = o, a plane of symmetry is equivalent to an S, axis. It is easy to see that a 180° rotation about an axis followed by reflection in a plane perpendicular to the axis is equivalent to inversion hence S2 = i, and a center of symmetry is equivalent to an S2 axis. 

All symmetry operations that we wish to consider can be regarded as either proper or improper rotations. 

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... 

The chief reason for pointing out these relationships is for systematization AO symmetry operations can be included in C. and S . Taken in the order in which they were introduced, c = S, i S2l E C,. Thus whoi we say that dural molecules are those without improper axes of rotation, the possibility of planes of symmetry and inversion centers has been included. 

It follows from Exercise 2.1-3(a) and Example 2.1-1 that the only necessary point symmetry operations are proper and improper rotations. Nevertheless, it is usually convenient to make use of reflections as well. However, if one can prove some result for R and IR, it will hold for all point symmetry operators. 

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. 

This is a most useful result since we often need to calculate the inverse of a 3 x3 MR of a symmetry operator R. Equation (10) shows that when T(R) is real, I R)-1 is just the transpose of T(R). A matrix with this property is an orthogonal matrix. In configuration space the basis and the components of vectors are real, so that proper and improper rotations which leave all lengths and angles invariant are therefore represented by 3x3 real orthogonal matrices. Proper and improper rotations in configuration space may be distinguished by det T(R),... 

It will be more economical in the first two sections to label the coordinates of a point P by xi x2 x3. Symmetry operations transform points in space so that under a proper or improper rotation A, P(xi x2 x3) is transformed into P (xi x x3 ). The matrix representation of this... 

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... 

There is another symmetry element or operation needed for discrete molecules, the improper rotation, S . A tetrahedron (the structure of... 

In molecules, there are five symmetry elements identity, mirror planes, proper rotation axes, improper rotation axes and inversion. A full explanation of these symmetry elements and their corresponding operators may be found in any standard chemistry textbook, and are shown diagramatically in Figure 8.13. 

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