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Representations of Molecular Properties

The document discusses representations of molecular properties using vectors located on each atom. It provides examples of how unit vectors (x, y, z) and rotational vectors (Rx, Ry, Rz) transform under the symmetry operations of the C2v point group. The vectors are classified according to the irreducible representations (A1, A2, B1, B2) they belong to based on their transformation properties. For example, the vector z transforms as the totally symmetric A1 representation, while the rotational vector Rz transforms as the A2 representation.

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KaPíl JêThwañì
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44 views11 pages

Representations of Molecular Properties

The document discusses representations of molecular properties using vectors located on each atom. It provides examples of how unit vectors (x, y, z) and rotational vectors (Rx, Ry, Rz) transform under the symmetry operations of the C2v point group. The vectors are classified according to the irreducible representations (A1, A2, B1, B2) they belong to based on their transformation properties. For example, the vector z transforms as the totally symmetric A1 representation, while the rotational vector Rz transforms as the A2 representation.

Uploaded by

KaPíl JêThwañì
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Representations of Molecular Properties

L We will routinely use sets of vectors located on each atom of a


molecule to represent certain molecular properties of interest (e.g.,
orbitals, vibrations).

T The set of vectors for a property form the basis for a


representation (or basis set).

T The mathematical description of the behavior of the vectors


under the symmetry operations of the group forms a
representation of the group.

T In most cases the representation for the property will be the


sum of certain fundamental representations of the group,
called irreducible representations.

L A representation is a set of symbols (called characters) that have


the same combinational results as the elements of the group, as
given in the group's multiplication table.

T Typical characters in representations of point groups include


the following:

0, 1, 2, 3, i = &1 , = exp(2i/n)
Irreducible Representations of C2v

Given the multiplication table:

C2v E C2 v v'
E E C2 v v'
C2 C2 E v' v
v v v' E C2
v' v' v C2 E

The following set of substitutions has the same combinational


relationships:
C2v E C2 v v'
1 1 1 1 1

C2v E = 1 C2 = 1 v = 1 v' = 1
E=1 1 1 1 1
C2 = 1 1 1 1 1
v = 1 1 1 1 1
v' = 1 1 1 1 1

L The substitution of all 1's, which can be made for any point group,
forms the totally symmetric representation, labeled A1 in C2v.
C2v E C2 v v'
A1 1 1 1 1
Irreducible Representations of C2v

The following set of substitutions also satisfies the multiplication table:


C2v E C2 v v'
2 1 1 -1 -1

C2v E = 1 C2 = 1 v = -1 v' = -1
E=1 1 1 -1 -1
C2 = 1 1 1 -1 -1
v = -1 -1 -1 1 1
v' = -1 -1 -1 1 1

These characters form the A2 irreducible representation of C2v:

C2v E C2 v v'
A2 1 1 -1 -1
Irreducible Representations of C2v

Two other sets of substitutions also satisfy the multiplication table,


forming the B1 and B2 irreducible representations of C2v:

C2v E C2 v v'
B1 1 -1 1 -1
B2 1 -1 -1 1

Any other set of substitutions will not work; e.g.

C2v E C2 v v'
-1 -1 1 1

C2v E = -1 C2 = -1 v = 1 v' = 1
E = -1 1 1 -1 -1
C2 = -1 1 1 -1 -1
v = 1 -1 -1 1 1
v' = 1 -1 -1 1 1

All results are wrong!


Basic Character Table

The collection of irreducible representations for a group is listed in a


character table, with the totally symmetric representation listed first:

C2v E C2 v v'
A1 1 1 1 1
A2 1 1 -1 -1
B1 1 -1 1 -1
B2 1 -1 -1 1

L The characters of the irreducible representations can describe the


ways in which certain vector properties are transformed by the
operations of the group.
Unit Vector Transformations

T Consider the effects of applying the operations of C2v on a unit


vector z. [Assume v = xz and v' = yz.]

z
y
z

Operation z becomes In matrix


notation
E z [+1]z
C2 z [+1]z
v z [+1]z
v' z [+1]z

T The four 1 x 1 transformation matrices, taken as a set, are


identical to the A1 irreducible representation of C2v.

C2v E C2 v v'
A1 1 1 1 1 z
Unit Vector Transformations

L "In C2v the vector z transforms as the A1 representation (the totally


symmetric representation).

OR

L "In C2v the vector z belongs to the A1 species (the totally symmetric
species)."

L The terms irreducible representation and species are synonymous


and therefore interchangeable.
Unit Vector Transformations

T Consider the effects of applying the operations of C2v on a unit


vector x.
z
y

x
x

Operation x becomes In matrix


notation
E x [+1]x
C2 -x [-1]x
v x [+1]x
v' -x [-1]x

T The four 1 x 1 transformation matrices, taken as a set, are


identical to the B1 irreducible representation of C2v.

C2v E C2 v v'
B1 1 -1 1 -1 x

L "In C2v the vector x transforms as B1."


Unit Vector Transformations

T Consider the effects of applying the operations of C2v on a unit


vector y.
z
y

y
x

Operation y becomes In matrix


notation
E y [+1]y
C2 -y [-1]y
v -y [-1]y
v' y [+1]y

T The four 1 x 1 transformation matrices, taken as a set, are


identical to the B2 irreducible representation of C2v.

C2v E C2 v v'
B2 1 -1 -1 1 y

L "In C2v the vector y transforms as B2."


Rotational Vector Transformations

T Consider the symmetry of a rotation about the z axis.

z
y

x
Rz

Operation Rz becomes In matrix


notation
E Rz [+1]Rz
C2 Rz [+1]Rz
v -Rz [-1]Rz
v' -Rz [-1]Rz

T The four 1 x 1 transformation matrices, taken as a set, are


identical to the A2 irreducible representation of C2v.

L "In C2v the vector Rz transforms as A2."


Character Table with Vector Transformations

C2v E C2 v v'
A1 1 1 1 1 z
A2 1 1 -1 -1 Rz
B1 1 -1 1 -1 x, Ry
B2 1 -1 -1 1 y, Rx

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