5.

04, Principles of Inorganic Chemistry II

MIT Department of Chemistry
Lecture 2: Operator Properties and Mathematical Groups

The inverse of A is B if A•B = E … for each operation

-1 =
…
•
= E
i-1 = I … i • i = E

(Cnm)-1 = Cnn-m … Cnm • Cnn-m = E (ex. (C52)-1 = C53 since C52 • C53 = E)
(Snm)-1 n even = Snn-m … Snm • Snn-m = Snn = E
(Snm)-1 n odd = Sn2n-m … Snm • Sn2n-m = Sn2n = E

Two operators commute when x•y = y•x

Example: Do C4(z) and
(xz) commute?

C4(z)
(xz)(x1, y1, z1)

y

(x1, y1)

x
(x2, y2) = (x1, -y1)
C4(z)(x 1, -y1, z1)
y

(x2, y2)

(x3, y3)=(-x1, -y1)

y

d’
d'

(x1, y1)

z1 does not change x C4(z)
(xz) =
d’

with
d’

(x3, y3)=(-x1, -y1)

5.04, Principles of Inorganic Chemistry II Lecture 2

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(xz) C4(z)(x1, y1, z1)
y

(x1, y1)

(x2, y2)=(-x1, y1)

(xz)(y 1, -x1, z1)

y
(x3, y3)=(x1, y1, z1)

d’ (x2, y2)

y (x3, y3)

C4(z)
(xz) =
d’ (x1, y1)

(xz)C4(z) =
d
x

so C4(z) does not
d

commute with
(xz)

A collection of operations are a mathematical group when the following

conditions are met:
closure: all binary products must be members of the group
identity: a group must contain the identity operator
inverse: every operator must have an inverse
associativity: associative law of multiplication must hold
(A • B) • C = A • (B • C)
(note: commutation not required… groups in which all operators
do commute are called Abelian)

5.04, Principles of Inorganic Chemistry II Lecture 2

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Consider the operators C3 and
v. Obviously not a group as identity criterion
are not satisfied. Do E, C3,
v form a group? To address this question, a
stereographic projection (featuring critical operators) will be used:

v plane normal to paper

signifies C3 (normal to paper)

How about closure?

v
v
v

C3 • C3 = C32
o o

v C3
C3 •
v = ? o

v'
o

C3 •
v =
v’

Thus E, C3 and
v are not closed and consequently these operators do not
form a group. what other operators are generated by C3 and
v?

… the proper rotation axis, C3:

C3

C3 • C3 = C32

C3 • C3 • C3 = C32 • C3 = C3 • C32 = E

C3 • C3 • C3 • C3 = E • C3 = C3

etc.

 C3 is the generator of E, C3 and C32

5.04, Principles of Inorganic Chemistry II Lecture 2

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… for the plane of reflection,
v

v

v •
v = E

v •
v •
v = E •
v =
v
etc.

so no new information here. But there is more information to be gained from

considering C3 and
v. Have already seen that C3 •
v =
v’ … how about

v • C3?

v
v
v

o
C3
v
o o

o
 C3 •
v =
v”

Will discover that no new operators may be generated. Moreover one finds
that

1  2 
1
1   -1   
1

E
1 C3 C3
v  v
 v

     
inverses      
2
E C3 C3  
v v v

The above group is closed, i.e. it contains the identity operator and meets
inverse and associativity conditions. Thus the above set of operators
constitutes a mathematical group (note that the group is not Abelian).

5.04, Principles of Inorganic Chemistry II Lecture 2

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Operators C3 and v are called generators for the group since every element
of the group can be expressed as a product of these operators (and their
inverses).

The order, h, of the group is the number of elements. In the above example,
h = 6.

Groups defined by a single generator are called cyclic groups.

Example: C3
E, C3, C32

Note that E, C3, and C32 meet the conditions of a group… they form a cyclic
group. Moreover these three operators are a subgroup of E, C3, C32, v, v’,v”.
The order of a subgroup must be a divisor of the order of its parent group.
(Example hsubgroup = 3, hgroup = 6 … a divisor of 2.)

5.04, Principles of Inorganic Chemistry II Lecture 2

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