Point groups definition

Vibrations may be decomposed into three orthogonal components Ta (a = x, y, z) in three directions. These displacements have the same symmetry properties as cartesian coordinates. Likewise, any rotation may be decomposed into components Ra. The i.r. spanned by translations and rotations must clearly follow the appropriate symmetry type of the point-group character table. In quantum formalism, a transition will be allowed only if the symmetry product of the initial and final-state wave functions contains the symmetry species of the operator appropriate to the transition process. Definition of the symmetry product will be explained in terms of a simple example. 

By definition, a molecule is achiral if it is left invariant by some improper operation (reflection or rotary reflection) of the point group of the skeleton. Writing the permutation s corresponding to a given improper operation in cyclic form,... 

An element of an electrostatic moment tensor can only be nonzero if the distribution has a component of the same symmetry as the corresponding operator. In other words, the integrand in Eq. (7.1) must have a component that is invariant under the symmetry operations of the distribution, namely, it is totally symmetric with respect to the operations of the point group of the distribution. As an example, for the x component of the dipole moment to be nonzero, p(r)x must have a totally symmetric component, which will be the case if p(r) has a component with the symmetry of x. The symmetry restrictions of the spherical electrostatic moments are those of the spherical harmonics given in appendix section D.4. Restrictions for the other definitions follow directly from those listed in this appendix. 

We have seen in the previous section that the definition of a set of OjS is intimately bound up with some choice of function space. The reader is cautioned, however, that not all function spaces can be used to define OjjS appropriate for a given point group. For example, the functions cosXi, sinx cosx and sinx, do not forma basis for a representation of the (symmetric tripod) point group xl and xt are the coordinates introduced before (see Fig. 5-2.2). 

Since it can be shown that "( ), like the original Hamiltonian H, commutes with the transformation operators Om for all operations R of the point group to which the molecule belongs, the MOs associated with a given orbital energy will form a function space whose basis generates a definite irreducible representation of the point group. This is exactly parallel to the situation for the exact total electronic wavefunctions. 

Let the functions F ...,FW form a basis for a representation of some point group. Since a symmetry operation R amounts to a rotation (and possibly a reflection) of coordinates, it cannot change the value of a definite integral over all space we have... 

Therefore, k+bm and k label the same representation and are said to be equivalent (=). By definition, no two interior points can be equivalent but every point on the surface of the BZ has at least one equivalent point. The k = 0 point at the center of the zone is denoted by T. All other internal high-symmetry points are denoted by capital Greek letters. Surface symmetry points are denoted by capital Roman letters. The elements of the point group which transform a particular k point into itself or into an equivalent point constitute the point group of the wave vector (or little co-group of k) P(k) C P, for that k point. 

The angular momentum components span a definite irreducible representation (IR) of the given point group (Table 9), and thus its matrix element vanishes unless the direct product of the IRs for the bra kets contains the IR of the Ifl-operator hence... 

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