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Element
E, the identity Does nothing
Operation
Example
All objects posses E
Rotate object by 2/n about the n-fold axis. The axis with the highest n is called the principle axis. For n>2 the sense is importantCn+ - clockwise rotationCn--counterclockwise rotation
H2O posses a C2 axis NH3 posses a C3 axis Benzene posses a C2, C3, C6, and two sets of three C2 axes perpendicular to the C6 axis
Reflects through the plane Plane containing the principle axis Plane perpendicular to the principle axis Vertical plane which bisects two C2 axes perpendicular to the principal axis H2O Benzene Benzene
Three types
d, dihedral plane
i, inversion center
Sends each atom through the origin along a straight line so that x-x, y-y, and z-z
Rotate object by 2/n, then reflects through plane perpendicular to the axis of rotation
CH4
One three-fold axis coincident with the C-C bond Three two-fold axes perpendicular to the C-C bond and intersecting its midpoint Three reflection planes, each containing the C-C bond and a pair of C-H bonds One reflection plane perpendicular to the C-C bond and bisecting it NO CENTER OF INVERSION IS PRESENT One three-fold improper axis coincident with the C-C bond
One three fold axis coincident with the C-C bond Three two-fold axes perpendicular to the C-C bond and intersecting its midpoint Three reflection planes, each containing the C-C bond and a pair of C-H bond No reflection plane perpendicular to the C-C bondwe lost it! One point of inversion at the midpoint of the C-C bondwe gained it! One six-fold improper axis coincident with the C-C bondchanged its order!
Stereographic Projections
Lets consider the symmetry elements of the C2v point group and the resulting symmetry operations
Still considering the symmetry elements of the C2v point group and the resulting symmetry operations
C2v
C2
v'
C2
v'
C2
C2
v'
v'
C2
v'
v'
C2
Lets try this with another point group and build the character table
C2h E E C2 h i
C2
i h C2 E
C2
Point Groups
Symmetry operations may be organized into groups that obey the four properties of mathematical groupsnamely 1. 2. 3. 4. There exists an identity operator that commutes with all other members The product of any two members must also be a member Multiplication is associative The existence of an inverse for each member
It will be possible to assign ANY molecule to one of these so-called Point Groups So named because the symmetry operation leaves one point unchanged
Point Groups
Point Group C1 Trivial group with contains all molecules having no symmetry There is no center of inversion, plane of reflection, improper axis of rotation, etc. The molecule HNClF (below) is such a molecule
Point Groups
Point Group Cs Only molecules which have to them a plane of reflection as a symmetry element Formyl Chloride belongs to this point group
Point Groups
Point Group Ci Molecules whose sole symmetry element is an inversion center As an example take the rotamer of 1,2-dichloro-1,2-diflouroethane in which the fluorine atoms are off-set to one another The only operations generated by this inversion are i and i2=Ethis is a group of order 2 and is designated Ci
Point Groups
Point Group Cn Molecules with only an n-fold axis of rotation Boric acid with the hydrogen atoms lying above the BO3 plane is an example
Point Groups
Point Group Cnv Molecules with an n-fold Cn axis of rotation and n vertical mirror planes which are colinear with the Cn axis Water belongs to such a point groupthe C2V
Note that if you find a Cn axis and one v plane then you are gauranteed to find n v planes
Point Groups
Point Group Cnh This point group is generated by a Cn axis of rotation AND a horizontal mirror plane, h, which is perpendicular to the Cn axis Trans-butadiene (trans-1,3-butene) is an example of the C2h point group
Point Groups
Point Group Dn This point group is generated by a Cn axis of rotation and a C2 axis which is perpendicular to the Cn axisno mirror planes Tris(ethylenediamine)cobalt(III) posses idealized D3 symmetry
Build this molecule and convince yourself that this in indeed the case!!
Point Groups
Point Group Dnd This point group is generated by a Cn axis of rotation and a C2 axis which is perpendicular to the Cn axis and a dihedral mirror plane, d The dihedral plane is colinear with the principal axis and bisects the perpendicular C2 axis Crystals of Cs2CuCl4 have a squashed tetrahedral D2d structure
Point Goups
Point Group Dnh This point group is generated by a Cn axis of rotation and n C2 axis which is perpendicular to the Cn axis and a horizontal mirror plane which is by definition perpendicular to the principal axis of rotation Benzene is the classic example, possesing D6h symmetry
Point Goups
Point Groups Sn These point groups are generated by an Sn axis. For example, the spirononanetetraflourospirononane belongs to the S4 point group and only elements generated by S4 S4 S42 = C2 S43 S44 = E The S2 point group is just Ci since S2 = i When n is odd the point groups are just the same as the Cnh point groups and so are designated as such As a direct result, only S4, S6, and S8, have a separate existence