II.

PointGroups
Point Group A complete set of symmetry operations that can be carried out on a single object (reflecting the overall symmetry of the object). These symmetry operations are called point group symmetry operations because they leave at least one point of the object unmoved. E nothing moved a whole plane not moved Cn a line not moved i (S2) a point not moved Objects (including molecules) that possess all symmetry operations of a given point group are said to belong to that (point) group.

Crystallographic Point Groups A set of point groups used to classify molecules (based on crystallography). There are 32 crystallographic point groups that classify most known molecules. (See pictures shown on next page) About 40 point groups classify all molecules (32 crystallographic groups listed on next page, plus a couple of others, including dodecahedron and icosahedron.

1. Assigning Molecules to Point Groups

(a) Point Group C1 Consisting of a single symmetry operation E ( = C1). Any molecules that do not have any real symmetry belong to this point group. Ex/. CHBrClF
F Cl Br H

32 Point Groups

(b) Point Group Cs Consisting of two and only two symmetry operations: E and . Any molecules that contain a reflection symmetry plane (only) belong to this point group. Ex/. CH(Cl2)F
Cl Cl F H

(c) Point Group Ci Consisting of two and only two symmetry operations: E and i. Any molecules that contain only a center of symmetry belong to this point group. Ex/. (CHBrCl)2 (staggered)
H Br Cl

Cl Br

(d) Point Group Cn Consisting of n symmetry operations: E, Cn , Cn2 Cnn-1 Any molecules that contain a n-fold symmetry rotational axis Cn belong to this point group. Ex/. H2O2 (Hydrogen Peroxide)
H H

or

C2

(e) Point Group Cnv (Cn as a subgroup) Consisting of 2n symmetry operations: E, Cn , Cn2 Cnn-1 , nv Molecules that have an n-fold rotational axis Cn and n v vertical reflection planes (passing the n-fold rotational axis Cn) belong to this point group (no C2 Cn). Ex/. H2O (2n = 4)
H O H

E, C2(z), v(xz), v(yz) E, C3(z), C32(z), v, v, v

z y

NH3 (2n = 6)

H H

(f) Point group Cnh (Cn as a subgroup) Consisting of 2n symmetry operations Molecules that have a Cn symmetry axis with a h symmetry reflection plane perpendicular to the Cn axis belong to this point group (no C2 Cn).
H

Ex/.
F

F
C C H

C2h (2n = 4): E, C2(z), h(xy), i

y x

H O
B

O H

C3h (2n = 6): E (= C33), C3(z), h(xy), C32, S3, S35 (S32 = C32, S33 = h, S34 = C3)

Also,

C1h = Cs

For n = even, Cnh has an inversion center (i) C2h, C4h, C6h

(g) Point Group Dn (Cn as a subgroup) Consisting of 2n symmetry operations. Molecules that have a Cn rotational axis and n C2 rotational axis perpendicular to the Cn axis belong to this point group. Ex/. Ethane (C2H6) (configuration that is neither a staggered nor eclipsed) C2 C2 H H The two equilateral H

H H

H H
C2

triangles are not symmetrically placed w.r.t. each other

E, C3, C32, 3C2 (h) Point Group Dnh (Dn as a subgroup) Consisting of 4n symmetry operations. Molecules that have a Cn axis, n C2 axes perpendicular to Cn, a horizontal symmetry plane (h) and n v vertical symmetry planes (passing through Cn) belong to this symmetry point group.

Ex/. BF3 (D3h), 4n = 12

F

symmetry elements: C3, h(xy), v, v, v, C2, C2, C2, S3

F

symmetry operations: E, C3, C3 2, S3, S32, v, v, v, h, C2, C2, C2 (Note: S33 = h)

For even n, Dnh has an inversion center i. (i) Point Group Dnd (Dn as a subgroup) Consisting of 4n symmetry operations. Molecules that have a Cn axis, n C2 axes perpendicular to Cn, and n d dihedral planes (passing through Cn) belong to this symmetry point group. Ex/. staggered ethane (D3d) C2
H H H

E, C3, C3 2, 2S6, d, d, d, C2, C2, C2 , i For odd n, Dnd has an inversion center i.

C2
H H H

C2

(j)

Point Group Sn (n = even) Consisting of n symmetry operations (Sn , Sn2 Snn = E) Molecules that have an Sn axis only without mirror planes belonging to this group. n = odd Sn Cnh group [since (Sn)n h and (Sn)2n E] Note: a) Dnd also contains Sn axis, but it also contains n d mirror planes b) S1 Cs C1h group (recall S1 operation h operation) c) A Sn axis may coincide with a Cn/2 axis Ex/. S4 point group: S4, S42 = C2 , S43 , E

(k) Linear Point Groups Cv: Containing symmetry operations: E, C , v Molecules that have a C axis, v vertical reflection planes, but no C2 axis perpendicular to the C axis belong to this group. All heteronuclear diatomic molecules, and all asymmetric linear polyatomic molecules belong to this point group (e.g. C-O, H-F, S-C-N-)

Dh: All symmetry operations in Cv plus C2 rotations perpendicular to the C axis, and a h plane. All homonuclear diatomic molecules and symmetric linear polyatomic molecules belong to this group. Ex/. O=C=O, NCC N, HCC H, NN (l) Point Groups Arised from Platonic Solids Platonic Solid polyhedra with all vertices, edges, and faces equivalent. In 3D space, five exist: Tetrahedron, Cube, Octahedron, Dodecahedron, Icosahedron (See next page). Conjugate of a Platonic Solid solid figure obtained by connecting the centers of adjacent faces in a platonic solid with lines Cubic Octahedron Tetrahedron Tetrahedron Icosahedron Dodecahedron No. Symmetry Operations = 2(No. Faces) (No. Edges Per Face)

Five Platonic Solids

TETRAHEDRON Four triangular faces, four vertices, and six edges.

(2 4 3 = 24)
CUBE Six square faces, eight vertices, and twelve edges.

(2 6 4 = 48)

OCTAHEDRON Eight triangular faces, six vertices, and twelve edges.

(2 8 3 = 48)

DODECAHEDRON Twelve pentagonal faces, twenty vertices, and thirty edges.

ICOSAHEDRON Twenty triangular faces, twelve vertices, and thirty edges.

Tetrahedron (Td) 24 symmetry operations: E, 8C3 , 3C2 , 6S4 , 6d Any molecules with a tetrahedral geometry belong to this group Ex/. Octahedron (Oh) 48 symmetry operations Any molecules with an octahedral symmetry belong to this group. Ex/. Cube (Th) 48 symmetry operations Any molecules with a cubic symmetry belong to this point group. Icosahedron and Dodecahedron (Ih) 120 symmetry operations Molecules that have one of these two symmetries (geometries) belong to this group. SF6 , (PtCl6)2CH4 , CCl4

(m) A systematic way to assign molecule to a point group Use Figure 4-7 (text p. 83) as a guide while assigning a molecule to a point group. First determine if the molecule is linear. Decide if there are two or more Cn with n > 2. Find the principal rotational axis Cn for molecules with only one Cn (n > 2). Work with each of the subgroups to determine the actual point group. PF5 (40 valence e-, trigonal bipyramidal) C3 and no other Cn with n > 2, 3C2 C3 , h D3h (no i)
F

Ex/. (a)

(b)

(AgC6H6)+ C6 , no other Cn with n > 2, No n C2 C6 , no h Yes 6 v C6v

F P F F
H

Ag

H H H

Point Group Assignment

III. SymmetryApplications
The symmetry of a molecule is crucial for certain properties to exist. Here we discuss two such properties.

1. Polarity
A molecule is polar if it has a permanent Electric Dipole Moment (), when summation of all individual Bond Moment Vector (b) is nonzero. Dipole Moment:

r = b = (q d b ) b = q db r r

+q

-q

db

Where,

q = charge db = distance between the two charge centers

Since a symmetry operation produces a configuration physically indistinguishable from the original one, the direction and the magnitude of the dipole moment vector must remain unchanged after a symmetry operation. Therefore, the dipole vector must be contained in all symmetry elements of the molecule that has a permanent dipole moment.

Important Notes For a proper rotation axis Cn must lie in the axis For two or more non-coincident symmetry axes no dipole (This excludes all point groups containing Dn as a subgroup) Ex/. CH4 (Td), 4C3 axes, no dipole For symmetry plane must lie in the plane. For several symmetry planes must lie along the line of intersection of these planes. Ex/. H2O, in C2 axis, which is also the intersection line of the two v planes For center of symmetry i no dipole (direction change) Ex/. Any atoms containing a center of symmetry do not have dipole Br moments, e.g. (CHBrCl)2 (Ci)
H Cl Cl H Br

Conclusion

Only molecules that belong to C1 , Cs , Cn or Cnv point groups possess dipole moments and they are polar.

Examples a) CHCl2F Cs dipole b) H2O2 C2 dipole

Cl Cl

(hydrogen peroxide)
H

or

C2

2. Chirality and Optical Activity

Chiral Molecule Molecule/object that is not superimposable on its mirror image (ex/ hands) Chiral Greek hand Enantiomer A chiral molecule and its mirror image together form a pair of enantiomers. Enantimer Greek both Chiral molecules are (potentially) optically active. They can rotate the plane of polarized light that passes through them.

How can we make use of symmetry to identify a molecule in terms of its optical activity? Consider a Sn symmetry operation on a molecule A: A
Cn

Rotated A

Mirror Image of (Rotated) A

Superimposable since Sn is a symmetry operation As shown above, an improper symmetry rotation Sn always converts a right-handed object into a left-handed one and they are superimposable. Thus, molecules containing any Sn axis can not be chiral, and they can not be optically active. Since: S1 , S2 i

Molecules having any plane of symmetry or center of symmetry can not be chiral, and they are optically inactive.

Conclusion Only molecules that belong to C1 and Cn point groups are potentially optically active. Examples: