Improper Rotations S6 for Oh

there are 6S4 operations o each pair of C4 axis and d mirror plane has an associated improper rotation, the S4 axis is coincident with the C4 axis. o Phase changes are important for improper rotations and it is best to work with pAOs rather than sAO when drawing out these operations. There are two sets of symmetry related orbitals; the equatorial and axial p orbitals. These subsets only transform amongst themselves under the S4, Figure 1
C4

!d

Figure 1 Sets of symmetry related orbitals

1 o Consider a S4 operation which consists of a rotation of 90 around a C4 axis and then 1 reflection in the associated h plane. An example of the S4 operation is given in Figure 2. 1 For simplicity the effect of the S4 operation has been shown for a single equatorial and axial p orbital. Notice that if you considered only the equatorial p orbitals you might conclude 1 that S4 = C2 !! , which would be incorrect.

C4

C4

C4

!d

C4

!d

2 1 S4 = C2

Figure 2

1 operation S4

o working through the various improper rotation symmetry operations results in identifying that 2 4 S4 = C2 and S4 = E , Figure 3, thus for each C4 axis (of which there are three) there are two 1 3 !1 unique S4 operations ( S4 ) and hence there are 6S4 operations in Oh. S4 = S4
C4 C4 C4

!d

1 S4

2 S4

C4

C4

3 S4

4 S4

Figure 3 All S4 operations

C3
L L M L L L
Figure 4

!h

there are 8 S6 operations o each C3 axis can also be thought of as having a coincident C6 and ! h mirror plane perpendicular to this axis. o these are not symmetry elements of Oh because of the staggered arrangement of the three ligands o in Figure 1, a simplified model is shown with has black dots on the sites that are occupied by ligands 1 o consider S6 , a rotation of 60 and then reflection in the associated ! h plane perpendicular to the axis, Figure 2 o all of the S6 operations are shown in Figure 3, 1 5 !1 only two are unique S6 and S6 . = S6 o thus for each C3 axis (of which there are four) there are two associated S6 operations and hence there are 8 S6 operations in Oh

C6

!h

1 S6
1 operation S6

Figure 5 Components of the

1 S6

2 S6

S63

4 S6 6 S6 5 S6

Figure 6 The S6 operations