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Chemistry · Glossary

What is Reducible representation, totally symmetric representation?

Also known as: reducible representation · totally symmetric representation

Definition 5.1 University Chemistry — Year 3 · Chapter 5 — Group Theory Applied

A reducible representation is one whose matrices can all be brought, by one change of basis, to the same block-diagonal form; it is then a sum of irreducible representations, written Γ=∑iniΓi\Gamma = \sum_in_i\Gamma_i. The irreducible representation whose characters are all 1 is the totally symmetric representation (A1A_1, A1gA_{1g}, A1′A_1'…).

Examples

Example 5.5 (The hydrogen orbitals of ammonia)

Take the three 1s1s orbitals of the hydrogens of NHX3\ce{NH3} as a basis. EE leaves all three in place (χ=3\chi = 3), C3C_3 moves all three (χ=0\chi = 0), a σv\sigma_v leaves one in place and swaps two (χ=1\chi = 1). With the C3vC_{3v} table: nA1=16(3+0+3×1)=1n_{A_1} = \frac16(3 + 0 + 3\times1) = 1, nA2=16(3+0−3)=0n_{A_2} = \frac16(3 + 0 - 3) = 0, nE=16(6+0+0)=1n_E = \frac16(6 + 0 + 0) = 1. So ΓH=A1+E\Gamma_{\mathrm H} = A_1 + E: the three hydrogens give one totally symmetric combination and a degenerate pair.

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