对称性与光谱学-第五章-1.pptVIP

Character Tables an Example C3v : (NF3) 4. Constructing the Representation ?v ?d C4,C2 E C4 C2 ?v ?d +Rz +Rz +Rz -Rz -Rz -1 -1 1 1 1 ?(Rz) 2 ?d’ 2?d C2 2C4 E The Rz forms a basis for ,or as transforms as, the A2 irreducible representation, Rx and Ry, together, form a basis for the E representation in C4v. Constructing the Representation Au Au Au sh sh.[d x2-y2] = (+1) .[d x2-y2] C4.[d x2-y2] = (-1) .[d x2-y2] C4 [AuCl4]- -1 +1 +1 -1 +1 -1 +1 +1 -1 +1 2sd 2sv sh 2S4 I 2C2” 2C2’ C2 2C4 E D4h For all the symmetry operations of D4h on [d x2-y2] We have: B1g * Chapter 5: Character Tables Instead of working with irreducible representations, we are going to make things even simpler and work with characters of irreducible representations. Character Tables Character , ? = a11 + a22 + a33. In general And only the character ?, which is a number is required and NOT the whole matrix. 1. Definition of characters Character=trace= 1+7+7+1+5=21 Inversion i z y x z1 y1 x1 i c(i) = -3 z1 y1 x1 x z y s(xz) Reflection s(xz) (Others are same except location of –1 changes) c(s(xz)) = +1 q q 360/n x1 y1 z1 z y x Cn Rotation Cn c(Cn) = 1 + 2.cos(360/n) c(Sn) = -1 + 2.cos(360/n) Improper rotation axis, Sn Cn s(xy) z y x z’ y’ x’ y1 x1 z1 There are theorems which tell how to find the characters for any irreducible representation of any point group, but we shall not be concerned with deriving these characters. All of the character tables needed for common chemical problems are given in Appendix. Rudimentary character table for the point group C3v The complete set of operations of the group The name of irreducible representations 2. The classes of operators C3v This simplifies further. Some operations are of the same class and always have the same character in a given irreducible representation Trying some similarity transformations We find C3 and C32 form one class, and ?, ?’, ?” form another class, and E, always is in a class by itself. In general: 1. Various ?v operations