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Group Theory Function Space

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Bharti Kapil
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17 views15 pages

Group Theory Function Space

Uploaded by

Bharti Kapil
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Function Space and Transformation Operator, OR

Symmetry

Molecular Symmetry Operations

Point Groups

matrix representations matrix representations homomorphic group of


from a position vector from sets of base vectors transformation
operators OR

matrix representations
of transformation
operators OR using
different function
spaces

matrix representations of point


groups
Function Space

• A function space is a collection or family of mathematical functions which obeys certain rules.
• These rules are similar to those which apply to the family of position vectors in physical space.

Consider a set of functions : f1, f2,…. belonging to a function space, then the following rules and definitions must hold true :

(1) The addition of any two functions must produce a third function belonging to the function space.
(2) The multiplication of any of the functions by a number must produce a function which also belongs to the function space.
(3) Any function which is a linear combination of f1, f2, … (i.e., a1f1 + a2f2 + … ) must belong to the function space.
(4) The scalar product of any two functions is defined as

(fi, fj) = ∫ fi*fj d𝜏

where integration is over all the variables of fi and fj.

(5) If n of the functions f1, f2, … fn are linearly independent (i.e., a1f1 + a2f2 + …. + anfn = 0 only if a1 = a2 = ….an = 0), then any of the other
functions of the space can be expressed as some linear combination of these n functions. Such function space is said to be n – dimensional.
(6) An n – dimensional function space is defined by specifying n mutually orthogonal, normalized, linearly-independent functions; they are
called as orthonormal basis functions.
Transformation Operators, OR

• A new group homomorphic or similar to the given point group is introduced, in which the elements are transformation
operators which operate on the functions of some function space.
• These transformation operators which correspond to the symmetry operation R are denoted by OR.

• Properties of OR :
(1) They are linear :
OR (αf) = α (ORf) α is any number and f is any function belonging to a function space.

(2) OR f = f ’ where f ’ also belongs to the function space.

• This set of transformation operators OR associated with the symmetry operations of a given point group will have a group table which is
structurally the same as the one for the point group.
If an n-dimensional function space is defined by the set of linearly-independent basis functions f 1, f2, … ,fi,… fn and if

these are functions of three Cartesian coordinates x 1, x2 and x3, then a transformation operator, OR ( corresponding to
symmetry operation, R) is defined as :

(OR fi)(x1’, x2’, x3’) = fi(x1, x2, x3) i = 1,2, …. n

A new function OR fi assigns the value of old function fi at x1, x2, x3 to the position x1’, x2’, x3’.

In general,
n
ORfk = Σ Djk (R) fj where k = 1,2, …. n
j=1
The D(R) so found will form an n-dimensional representation of both the point group and the group of
transformation operators, OR.
Determining ORs and D(R)s for the C3v point group

A set of five d – orbitals is used to define a function space.


• d - orbitals can be expressed as Ψr, θ, φ = Rr Y θ, φ

• Ylm (θ, φ) is called spherical harmonics. For d- orbitals, l = 2, m = 0, ±1, ±2

• If we shift the point r, θ and φ to r’, θ’ and φ’, the resulting Ylm(θ’, φ’) can be expressed as linear combination of all the Y lm’(θ, φ) of
the same l value (m’= 0, ±1, ±2,…. ±l ) .
• ORYlm(θ’, φ’) = Ylm(θ, φ) (definition of OR)

= a linear combination of Ylm’(θ, φ) , m’= 0, ±1, ±2,…. ±l

• ORYlm = a linear combination of Ylm’


5

ORdi = Σ Dji (R) dj where d1, d2, ….. d5 are real d-orbitals.
j=1

The D(R) will form a representation of the point group.


• The five d-orbitals are defined by the equations :
d1= (x12 - x22) /2
d2 = x 1 x2
d3 = x 1 x3
d4 = x2 x3
d5 = (3x32 - r2)/ (2√3)
Rotation by an angle θ
Rotation
x1, x 2, x 3 x 1’,x2’, x3’
( along e3 axis )

x1 = d cos φ = d cos (φ- θ+ θ)


x1 = d cos (φ- θ) cos θ - d sin (φ- θ) sin θ
x1 = d (x1’/d) cos θ - d (x2’/d) sin θ clockwise rotation by θ

x1 = x1’ cos θ - x2’ sin θ


anti-clockwise rotation by θ

x2 = x1’ sin θ + x2’ cos θ

x 3 = x 3’

Oθ d1(x1’, x2’, x3’) = d1(x1, x2, x3)


= (x12 - x22)/2
= [{x1’ cos θ - x2’ sin θ }2 - {x1’ sin θ + x2’ cos θ}2]/2
= (cos 2θ) (x1’2 - x2’2)/2 - (sin 2θ) x1’x2’
= (cos 2θ) d1(x1’, x2’, x3’) - (sin 2θ) d2(x1’, x2’, x3’)
Oθ d1 = (cos 2θ) d1 - (sin 2θ) d2
Similarly,
Oθ d2 = (sin 2θ) d1 + (cos 2θ) d2
Oθ d3 = (cos θ) d3 - (sin θ) d4
Oθ d4 = (sin θ) d3 + (cos θ) d4
Oθ d5 = d5

5
Oθ di = Σ Dji (θ) dj
j=1
When θ = 2𝞹/3

When θ = 4𝞹/3
Reflection in σv planes
For σv’’ plane

inverse

d1(x1, x2, x3) = (x12 - x22)/2 = {(1/2x1’- √3/2x2’)2 - (- √3/2x1’ - 1/2x2’)2}/2


= -1/2(x1’2 - x2’2)/2 - √3/2x1’x2’
= -1/2 d1(x1’, x2’, x3’) - √3/2 d2(x1’, x2’, x3’)

d2(x1, x2, x3) = x1x2 = (1/2x1’- √3/2x2’) ((- √3/2x1’ - 1/2x2’)


= - √3/2 d1(x1’, x2’, x3’) + 1/2 d2(x1’, x2’, x3’)

d3(x1, x2, x3) = x1x3 = 1/2 d3(x1’, x2’, x3’) - √3/2 d4(x1’, x2’, x3’)

d4(x1, x2, x3) = x2x3 = - √3/2 d3(x1’, x2’, x3’) -1/2 d4(x1’, x2’, x3’)

d5(x1, x2, x3) = (3x32 - r2)/ (2√3) = d5(x1’, x2’, x3’)


Oσ d1(x1’, x2’, x3’) = d1(x1, x2, x3)
v’’
= -1/2 d1 - √3/2 d2
Similarly,
Oσ d2(x1’, x2’, x3’) = - √3/2 d1 + 1/2 d2
v’’

Oσ d3(x1’, x2’, x3’) = 1/2 d3- √3/2 d4


v’’

Oσ d4(x1’, x2’, x3’) = - √3/2 d3 -1/2 d4


v’’

Oσ d5(x1’, x2’, x3’) = d5


v’’

5
Oσ di = Σ Dji (σv’’) dj
v’’

j=1

We get
Similarly, it can be shown that :
Identity Element, E
Define function space

Determine relation between old coordinates and


coordinates obtained on applying symmetry operation

Apply transformation operator on functions of the


function space to determine new functions in terms of
old functions

Determine the matrix for D(R) which is characteristic


of the symmetry operation R using the equation
n
ORfk = Σ Djk (R) fj
j=1

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