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Symmetry Operations
A symmetry operation transforms an object into an
indistinguishable form. The center of mass does not move. The main types
of symmetry operation are:
E - identity
Cn - rotation by 2/n, where n is an integer
v - mirror plane containing the principal axis
d - mirror plane containing the principal axis and the bisector between C2
axes perpendicular to the principal axis. This is a property of higher-
symmetry figures (e.g., benzene, methane).
h - mirror plane perpendicular to the principal axis
i - inversion in the center of mass (i.e., x,y,z -x,-y,-z)
Sn - rotation by 2/n followed reflection in a plane perpendicular to the
symmetry axis. Sometimes called an improper rotation. Also, the reflection
plane does not have to be a symmetry plane of the figure. (Note that S2
inversion).
There are also some special point groups for linear molecules:
HCN and CO2
Point groups Cv, Dh respectively Here, we relabel the irreducible
representations according to the same nomenclature for the molecular term
symbols of linear molecules (see later): g,u, g,u etc.
Also, we find symmetry operations such as C and C2, in addition to some of
the more usual ones such as E, v and h.
http://www.webqc.org/symmetrypointgroup-c2v.html
8
Matrix multiplication table
Here is a matrix multiplication table for the point group C2v (e.g., water).
This shows the effects of sequential operations. Some are easy to see from
simple diagrams, whereas others are less obvious.
H H
O y
The table is symmetric, which means that all of the operators commute the order in
which operators are applied is irrelevant. This defines an Abelian group.
An important property of a group is that any sequence of operations is
equivalent to a single operation by any member of the group. Thus, the
elements in the multiplication table are all group members.
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Lets summarize the effects of applying the symmetry operations on the
different Cartesian axes of the water molecule:
plane of molecule
The top three lines in the above table are irreducible representations,
whereas their sum, the fourth line is a reducible representation.
Each number in the table represents the trace of a matrix for a particular
symmetry operation. That is, each symmetry operation is a mathematical
operation. The numbers in the top three lines represent 1-D matrices and
those in the bottom row, 3-D matrices.
Each 3-D transformation matrix in the point group C2v can be expressed as
the direct sum of three 1x1 matrices, which is expressed in block diagonal
form.
Note that there are no off-diagonal elements in any of the matrices. This tells us
that each matrix can be broken down as a sum of three different 1x1 matrices.
That is, the x, y & z axes have distinct symmetry properties in this point group.
Each matrix is reducible, which means that the representation (x+y+z) is
reducible. The matrices representing
11/27/2016 x, Group
Symmetry and y andTheory
z individually are all irreducible.
11
When these matrices are multiplied together, the results are the same as when
the operations are performed consecutively. For example, when we perform
C2 and then v (yz) , the matrix representation is:
v(yz) C2 v(xz)
Maple:
H H
H C2 C4
1 C C3 H
H H
http://www.webqc.org/symmetrypointgroup-c2h.html
http://www.webqc.org/symmetrypointgroup-d3h.html
Fixed point P:
Old coords: P (x,y)
New coords: P(x,y)
r New x axis
Rotate axes by
an angle
Old x axis
The TRACE of the matrix (sum of the NW-SE diagonal elements) is the same for
the same type of operator, independently of the choice of coordinate system.
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In 3-D:
Here the trace refers to a basis of three Cartesian vectors (or a set of p-orbitals).
It could be different for some other property (such as molecular vibrations) as
is readily seen from character tables (see below).
Different symmetry operations have distinct matrices, the value of the trace
depending on the context (see supplement):
Note that adding the extra dimension to accommodate the z-axis in effects adds
a 1x1 matrix along the diagonal to the original matrix. The new matrix is
11/27/2016 whereas the component
reducible, Symmetrymatrices
and Groupare irreducible.
Theory 19
The 3x3 matrix below is the sum of a 2x2 for the xy axes and a 1x1 for the z-
axis, having traces -1 and 1, respectively.
This three-fold axis is a key determining factor to the degeneracy of the x and y
axes. Thus, any property of a D3h molecule such as BF3 can be understood in
terms of a pair of equivalent axes (x,y) and a unique axis (z).
p2 p4
p1 p3
We are concerned only with the trace the sum of the diagonal elements.
The diagonal elements are only non-zero if the orbitals stay in place or are,
at most, inverted. Thus:
Each irreducible representation of a given point group is unique, each one has a
symmetry label, such as Ag, and there is a definite number of them.
Note the mistake in M &S p. 486, where they mislabel the h operation as v.
Basically multiply the two representations (i.e., one reducible and one
irreducible), character by character for each one of the symmetry operations R ,
and divide the result by the dimensionality, h, of the point group.
Test Example how many times does Ag appear in the RR for the MOs:
h=4
Also:
Etc.
B2g
E2u
E1g
A2u
O O
H H H H
O O
H H H H
Vib symm str; a1 Vib bend; a1
y
z O z
y y
HA HB
We take the x-axis to be out of the molecular plane.
HA HB O
x
y
HA
z
HB
11/27/2016 xSymmetry
y andz Group Theory 36
9x9 Matrix Describing the C2 operation on the x,y,z Atomic Vectors of Water
Instruction:
Exchange positions of
atoms HA and HB, and invert
the x and y vectors of each
Keep O2
atom where
it is , but
invert x and
y vectors
We are only
concerned with the
trace, which here is -1.
Therefore, we can
usually compute the
trace by simple
inspection
Tr(C2) = -1
Tr(v(xz)) = +1
Similarly:
Tr(E) = +9
Tr(v(yz)) = +3
11/27/2016 Symmetry and Group Theory 39
The traces of the 9x9 matrices for each symmetry operation are entered
as the characters of the reducible representation ((total)) in the C2v
character table.
As before, we can find the component IRs of the RR (total) either manually via the
method of Slide 25 (and M&S Equation 12.23 and Example 12-12), or we could have
Maple do it for us by vector multiplication (Slide 26).
A1 3650 cm-1
B2 3750 cm-1
( )
final H ' initial = symmetric
We can simplify the idea greatly by recognizing that, in an infrared spectrum,
the molecules are usually starting from the zero-point level. This is a symmetric
state, corresponding to the most symmetric representation of the molecular
point group (i.e., the top line of the character table, usually designated A1, Ag or
something similar). In order for the remaining two items to generate a
symmetric result, they must correspond to the same symmetry representation.
11/27/2016 Symmetry and Group Theory 46
If the operator is an electric dipole operator, which is the case for a 1-photon
transition, then it can be taken to have the same symmetry species as one of the
Cartesian axes.
Suppose we have a B2 vibrational mode in the water molecule. This will
correspond to the condition: final = B2. The above symmetry relationship requires
that () = B2, since B2 x B2 x A1 = A1. This can be checked by multiplying the
rows of the different representations, operation by operation.
This result shows that the transition from the zero-point energy to the B2
vibrational mode can be facilitated by a y-polarized photon. Normally, we dont
care which polarization is involved, as long as there is a fit.
Bottom line. A vibrational mode (or a rotation) will appear in the infrared
(or microwave) spectrum if the representation corresponding to that mode also
matches one of the three Cartesian axes. Its as simple as that.
Ground state
Virtual level
In Raman spectroscopy, since we
have a two-photon process, the
transformation is represented by
the quadratic products of x, y Raman-scattered
Laser photon
and z. Such modes would be photon
Raman active.
+1
} RRs for trans, rot and
vib degrees of freedom
Because of the 3-fold axis, there are some 2-D irreducible representations (IRs).
Mutual Exclusion Rule for centrosymmetric molecules: Vibrational modes can be IR active or
11/27/2016 Symmetry and Group Theory 55
Raman active, or neither. However, no mode can be both Raman and IR active.
Ethylene does not have a pure-rotation (microwave) spectrum.
The rotations all have g symmetry and do not correspond to the Cartesian vectors, which
are all u. It needs a permanent dipole moment to have a microwave spectrum.
+1
Gas
Liquid