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5.04 Principles of Inorganic Chemistry II ��
Fall 2008

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04. Principles of Inorganic Chemistry II Prof. σ σ (xz)(x1. The collection of objects is commonly referred to as a basis set J classify objects of the basis set into symmetry operations J symmetry operations form a group J group mathematically defined and manipulated by group theory A symmetry operation moves an object into an indistinguishable orientation A symmetry element is a point. vibrations). which will be defined relative to point with coordinate (x1. E E(x1. Daniel G. Daniel G.z1 ) 5.z1 ) = (x1. y1. z1 ) 2) plane of reflection. z1 ) = (x1. Principles of Inorganic Chemistry II Prof. Nocera Lecture 1 Page 1 of 5 . atoms of a molecule. line or plane about which a symmetry operation is performed There are five symmetry elements. set of orbitals.g. y1. Nocera Lecture 1: Symmetry Elements and Operations Consider the symmetry properties of an object (e. y1. y1.−y1. z1 ) : 1) identity.5.04.

z1 ) = σ (xy) C4 (z)(x1. Sn two step operation: Cn followed by σ through plane ⊥ to Cn S4 (z)(x1.−y1. Principles of Inorganic Chemistry II Prof. Cn (where θ = 2π ) n convention is a clockwise rotation of the point C2 (z)(x1. y1.04. Nocera Lecture 1 Page 2 of 5 . Corollary is that axes rotate counterclockwise relative to fixed point In the example above.z1 ) = (− x1. z1 ) = σ (xy)(y1.y1.z1 ) 5) improper rotation axis. we took the direct product of two operators: σ h ⋅ Cn = Sn for n even : Sn = Cn ⋅ σ h = E ⋅ E = E for n odd: Sn = Cn ⋅ σ h = E ⋅ σ h = σ h Sn 2n n n n n n n Horizontal mirror plane (normal to Cn) = Cn = Cn 2n ⋅ σh ⋅ σh 2n = E ⋅ E = σh = Cn m for m even: Sn for m odd: Sn m m m m = Cn m ⋅ σh m = Cn m ⋅ σ h = Sn m 5.z1 ) = (− x1.–x1. Daniel G.3) inversion.−y1. y1.y1.−x1 − z1 ) Note: rotation of pt is clockwise. i i (x1.−z1 ) 4) proper rotation axis. z1 ) = (y1.

v Symmetry operations may be represented as matrices. Consider the vector v Convention is that the principal axis of rotation (rotation axis with highest n) positioned to be coincident with the z axis x1 ⎤ ⎡ ⎡ ⎢ ⎥ ⎢ 1) identity: E ⎢y1 ⎥ = ⎢ ⎢ z1 ⎥ ⎣ ⎦ ⎢ ⎣ ? ⎤ ⎥ ⎥ ⎥ ⎦ x1 ⎤ ⎡x1 ⎤ ⎡ ⎢ ⎥ ⎢ ⎥ ⎢y1 ⎥ = ⎢y1 ⎥ ⎢ ⎣ z1 ⎥ ⎦ ⎢ ⎣ z1 ⎥ ⎦ ⎡1 0 0 ⎤ ⎥ ⎢ matrix satisfying this condition is: ⎢0 1 0 ⎥ ⎢ ⎥ 0 0 1 ⎣ ⎦ ⎡1 0 0 ⎤ ⎥ ⎢ ∴ E = ⎢0 1 0 ⎥ … E is always the unit matrix ⎢ ⎥ ⎣0 0 1 ⎦ x1 ⎤ ⎡ x1 ⎤ ⎡ ⎢ ⎥ ⎢ ⎥ 2) reflection: σ (xy) ⎢y1 ⎥ = ⎢ y1 ⎥ ⎢ z1 ⎥ − z1 ⎥ ⎣ ⎦ ⎢ ⎣ ⎦ 0 0 ⎡1 ⎤ ⎢ ⎥ similarly σ (xz) = ⎢0 − 1 0 ⎥ ⎢ ⎥ 0 0 1 ⎦ ⎣ ⎡1 0 0⎤ ⎢ ⎥ ∴ σ (xy) = ⎢0 1 0⎥ ⎢ ⎣0 0 − 1⎥ ⎦ ⎡− 1 0 0⎤ ⎥ σ (yz) = ⎢ ⎢ 0 1 0⎥ ⎢ ⎥ ⎣ 0 0 1 ⎦ and x1 ⎤ ⎡− x1 ⎤ ⎡ ⎢ ⎥ ⎢ ⎥ 3) inversion: i ⎢y1 ⎥ = ⎢− y1 ⎥ ⎢ z1 ⎥ ⎣ ⎦ ⎦ ⎢ ⎣ − z1 ⎥ ∴ 0 0⎤ ⎡− 1 ⎥ ⎢ i = ⎢ 0 − 1 0⎥ ⎢ 0 − 1⎥ ⎣ 0 ⎦ 5.04. Principles of Inorganic Chemistry II Prof. Daniel G. Nocera Lecture 1 Page 3 of 5 .

04. 73 solves for the counterclockwise rotation… and presents the clockwise result derived above. 5. Principles of Inorganic Chemistry II Prof. as discussed by HB (pg 39). Nocera Lecture 1 Page 4 of 5 . is not transformed under Cn(θ) ∴ projection into xy plane need only be considered… i. rotation of vector v(xi.4) proper rotation axis: because of convention. Daniel G. and hence zi. Cotton on pg. φ. To be consistent with HB (and math classes) we will rotate clockwise as the convention.yi) through θ v v v x1 = v cos α x2 = v cos [− (θ − α )] = v cos (θ − α ) Cn (θ ) ⎯⎯⎯ ⎯ ⎯→ v v v y1 = v sin α y2 = v sin [− (θ − α )] = – v sin (θ − α ) using identity relations: v v v x2 = v cos (θ − α ) = v cos θ cos α + v sinθ sin α = x1 cos θ + y1 sinθ v v v y2 = – v sin (θ − α ) = −[v sinθ cos α − v cos θ sinα ] = −x1 sinθ + y1 cosθ Reformulating in terms of matrix representation: x1 ⎤ ⎡ x1 cos θ + y1 sin θ ⎤ ⎡ ⎢ ⎥ ⎢ ⎥ Cn(θ ) ⎢y1 ⎥ = ⎢− x1 sin θ + y1 cos θ ⎥ ⎢ ⎥ z1 ⎥ z1 ⎣ ⎦ ⎢ ⎣ ⎦ ⎡ cos θ ⎢ ∴ Cn(θ ) = ⎢ − sin θ ⎢ ⎣ 0 0⎤ ⎥ cos θ 0⎥ 0 1⎥ ⎦ sin θ 2π n where θ = Note… the rotation above is clockwise.e..

04. Nocera Lecture 1 Page 5 of 5 . matrix operations may be manipulated with simple matrix algebra…above direct product yields matrix representation for Sn. Daniel G. Another example: 0 − 1 0 0 − 1 0 0 ⎡1 0 ⎤ ⎡ ⎤ ⎡ ⎤ ⎥ ⎢ ⎥ ⎢ ⎥ ⎢ 0⎥ ⋅ ⎢ 0 − 1 0 0⎥ ⎥ = ⎢ 0 − 1 ⎢0 1 ⎢ 0 1⎥ 0 − 1⎥ ⎣0 0 − 1⎥ ⎦ ⎢ ⎦ ⎣ 0 ⎦ ⎢ ⎣ 0 σ xy (≡ σ h ) ⋅ C2 (z) = i 5.The above matrix representation is completely 2π Example: C3 . θ = n 2π 2π 3 ⎡ ⎤ ⎡ 1 sin 0 ⎢ cos ⎥ ⎢ − 3 3 2 ⎢ ⎥ ⎢ 2 ⎢ ⎢ ⎥ 2π 2π 3 1 C3 = ⎢ − sin cos 0 − ⎥ = ⎢− 3 3 2 ⎢ ⎥ ⎢ 2 ⎢ ⎢ ⎥ ⎢ ⎥ ⎢ 0 0 0 1 0 ⎢ ⎥ ⎣ ⎦ ⎢ ⎣ 5) improper rotation axis : general for any rotation θ… ⎤ 0 ⎥ ⎥ ⎥ ⎥ 0 ⎥ ⎥ ⎥ 1 ⎥ ⎦ σh ⎡1 ⎢ ⎢0 ⎢ ⎣0 0 ⋅ Cn (θ ) = Sn (θ ) 0⎤ ⎥ cos θ 0 ⎥ 0 − 1⎥ ⎦ sin θ 0 ⎤ ⎡ cos θ ⎥ ⎢ 1 0 ⎥ ⋅ ⎢ − sin θ 0 − 1⎥ ⎣ 0 ⎦ ⎢ sin θ 0 ⎤ ⎡ cos θ ⎥ ⎢ cos θ 0 ⎥ = ⎢ − sin θ ⎥ 0 1 ⎦ ⎢ ⎣ 0 Like operators themselves. Principles of Inorganic Chemistry II Prof.

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