Point groups examples

Point group Example rlCO) modes Stretching Force constants Interaction... 

Molecular point group Example Infrared Raman... 

Coordination nnmber Shape Point group Examples... 

The function / is identified as being related to some symmetry point group. (Examples are given shortly.) We want to know what representation / is a basis for. If / produces a representation containing A, then / has some totally symmetric character and the integral need not vanish. But if / is devoid of Ai character, the integral vanishes by symmetry since all other representations are antisymmetric for at least one operation. Our problem, therefore, is to decide which irreducible representations are present in the representation that is produced by the integrand /. 

As an example, we again consider the PH molecule. In its pyramidal equilibrium configuration PH has all tlnee P-H distances equal and all tlnee bond angles Z(HPH) equal. This object has the point group synnnetry where the operations of the group are... 

As an example we consider the group introduced in (equation Al.4,19) and the point group given in (equation Al.4.22). Inspection shows that the multiplication table of in table Al.4,2 can be obtained from the multiplication table of the group (table Al.4,1) by the following mapping ... 

We now turn to electronic selection rules for syimnetrical nonlinear molecules. The procedure here is to examme the structure of a molecule to detennine what synnnetry operations exist which will leave the molecular framework in an equivalent configuration. Then one looks at the various possible point groups to see what group would consist of those particular operations. The character table for that group will then pennit one to classify electronic states by symmetry and to work out the selection rules. Character tables for all relevant groups can be found in many books on spectroscopy or group theory. Ftere we will only pick one very sunple point group called 2 and look at some simple examples to illustrate the method. 

This is the central Jahn-Teller [4,5] result. Three important riders should be noted. First, Fg = 0 for spin-degenerate systems, because F, x F = Fo. This is a particular example of the fact that Kramer s degeneracies, aiising from spin alone can only be broken by magnetic fields, in the presence of which H and T no longer commute. Second, a detailed study of the molecular point groups reveals that all degenerate nonlinear polyatomics, except those with Kramer s... 

If the symmetries of the two adiabatic functions are different at Rq, then only a nuclear coordinate of appropriate symmeti can couple the PES, according to the point group of the nuclear configuration. Thus if Q are, for example, normal coordinates, xt will only span the space of the totally symmetric nuclear coordinates, while X2 will have nonzero elements only for modes of the correct symmetry. 

If the states are degenerate rather than of different symmetry, the model Hamiltonian becomes the Jahn-Teller model Hamiltonian. For example, in many point groups D and so a doubly degenerate electronic state can interact with a doubly degenerate vibrational mode. In this, the x e Jahn-Teller effect the first-order Hamiltonian is then [65]... 

For example, the three NH bonding and three NH antibonding orbitals in NH3, when symmetry adapted within the C3V point group, cluster into ai and e mos as shown in the Figure below. The N-atom localized non-bonding lone pair orbital and the N-atom Is core orbital also belong to ai symmetry. 

In a second example, the three CH bonds, three CH antibonds, CO bond and antibond, and three 0-atom non-bonding orbitals of the methoxy radical H3C-O also cluster into ai and e orbitals as shown below. In these cases, point group symmetry allows one to identify degeneracies that may not have been apparent from the structure of the orbital interactions alone. 

That no degenerate molecular orbitals arose in the above examples is a result of the fact that the C2v point group to which H2O and the allyl system belong (and certainly the... 

It is assumed that the reader has previously learned, in undergraduate inorganie or physieal ehemistry elasses, how symmetry arises in moleeular shapes and struetures and what symmetry elements are (e.g., planes, axes of rotation, eenters of inversion, ete.). For the reader who feels, after reading this appendix, that additional baekground is needed, the texts by Cotton and EWK, as well as most physieal ehemistry texts ean be eonsulted. We review and teaeh here only that material that is of direet applieation to symmetry analysis of moleeular orbitals and vibrations and rotations of moleeules. We use a speeifie example, the ammonia moleeule, to introduee and illustrate the important aspeets of point group symmetry. 

For a function to transform according to a specific irreducible representation means that the function, when operated upon by a point-group symmetry operator, yields a linear combination of the functions that transform according to that irreducible representation. For example, a 2pz orbital (z is the C3 axis of NH3) on the nitrogen atom... 

The functions put into the determinant do not need to be individual GTO functions, called Gaussian primitives. They can be a weighted sum of basis functions on the same atom or different atoms. Sums of functions on the same atom are often used to make the calculation run faster, as discussed in Chapter 10. Sums of basis functions on different atoms are used to give the orbital a particular symmetry. For example, a water molecule with symmetry will have orbitals that transform as A, A2, B, B2, which are the irreducible representations of the C2t point group. The resulting orbitals that use functions from multiple atoms are called molecular orbitals. This is done to make the calculation run much faster. Any overlap integral over orbitals of different symmetry does not need to be computed because it is zero by symmetry. 

Figure 4.11 Examples of molecules belonging to various point groups...

Examples are rare except for the S2 point group. This point group has only an S2 axis but, since S2 = i, it has only a centre of inversion, and the symbol generally used for this point group is C,. The isomer of the molecule ClFHC-CHFCl in which all pairs of identical FI, F or Cl atoms are trans to each other, shown in Figure 4.11(b), belongs to the C, point group. 

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