配位化学【双语版】Chapter 2.pptx

Chapter 2 Electronic Structure Theory of Coordination CompoundFocus on Transition metal coordination chemistryThe atomic structureSymmetry in Chemistry – Group TheoryGroup Theory?is one of the most powerful mathematical tools used in Quantum Chemistry and Spectroscopy. It allows the user to predict, interpret, rationalize, and often simplify complex theory and data. At its heart is the fact that the?Set of Operations?associated with the?Symmetry Elements of a molecule constitute a mathematical set called a?Group. This allows the application of the mathematical theorems associated with such groups to the?Symmetry Operations.All?Symmetry Operations?associated with isolated molecules can be characterized as Rotations: (a)?Proper Rotations: Cnk; k = 1,......, n?When k = n, Cnk?= E, the Identity Operation?n indicates a rotation of 360/n where n = 1,.... (b)?Improper Rotations: Snk?, k = 1,....., n?When k = 1, n = 1 Snk?= s , Reflection Operation?When k = 1, n = 2 Snk?= i , Inversion Operation In general practice we distinguish?Five?types of operation: (i)?E, Identity Operation (ii)?Cnk?, Proper Rotation about an axis (iii)?s, Reflection through a plane (iv)?i, Inversion through a center (v)?Snk, Rotation about an axis followed by reflection through a plane perpendicular to that axis.Each of these?Symmetry Operations?is associated with a?Symmetry Element?which is a point, a line, or a plane about which the operation is performed such that the molecules orientation and position before and after the operation are indistinguishable.The?Symmetry Elements?associated with a molecule are: (i) A?Proper Axis of Rotation: Cn?where n = 1,....?This implies n-fold rotational symmetry about the axis.(ii) A?Plane of Reflection: s?This implies bilateral symmetry about the plane.?These planes are further classified as:sh?- Horizontal Plane?which is perpendicular to the Principal Axis of Rotation (i.e. Axis with highest value of n). If no principal axis exists sh?is defined as the molecula