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Chemistry · Glossary

What is Projection operator?

Definition 5.7 University Chemistry — Year 3 · Chapter 5 — Group Theory Applied

The projection operator onto the irreducible representation Γi\Gamma_i is

P^i=dih∑Rχi(R)∗ R^,\hat P_i = \frac{d_i}{h}\sum_R\chi_i(R)^*\,\hat R,

where R^\hat R applies the operation RR to a function.

Examples

Example 5.10 (The combinations of ammonia and water)

In NHX3\ce{NH3}, P^A1h1∝h1+h2+h3\hat P_{A_1}h_1 \propto h_1 + h_2 + h_3 (all characters 1). For EE (characters 2,−1,02, -1, 0), P^Eh1∝2h1−h2−h3\hat P_Eh_1 \propto 2h_1 - h_2 - h_3; projecting h2h_2 and orthogonalising gives the partner h2−h3h_2 - h_3. Normalised: a1=13(h1+h2+h3)a_1 = \frac{1}{\sqrt3}(h_1 + h_2 + h_3), e=16(2h1−h2−h3)e = \frac{1}{\sqrt6}(2h_1 - h_2 - h_3), 12(h2−h3)\frac{1}{\sqrt2}(h_2 - h_3). In HX2O\ce{H2O}, placed in the xzxz plane, h1+h2h_1 + h_2 is a1a_1 and h1−h2h_1 - h_2 is b1b_1 (it changes sign under C2C_2 and under σv′(yz)\sigma_v'(yz), which exchange the hydrogens). With the molecule in the yzyz plane, as some books prefer, the labels b1b_1 and b2b_2 are exchanged throughout.

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