(c) Symmetry

adapted
linear
combinations
Symmetry adapted linear
combinations (SALC)
• SALC is a combination of orbitals constructed from equivalent atoms and having a specified
symmetry.
• SALCs are very useful in constructing molecular orbitals because a given SALC has non-zero
overlap only with other orbitals of the same symmetry.
• The technique for building SALCs involves the use of a projection operator, P(Γ).
Example: Construct the B1 symmetry-adapted linear combination of O2px orbitals for NO2

E C2 V(xz) ’V(yz)
Example: Construct the B1 symmetry-adapted linear combination of O2px orbitals for NO2

E C2 V(xz) ’V(yz)

Effect on PA
Example: Construct the B1 symmetry-adapted linear combination of O2px orbitals for NO2

E C2 V(xz) ’V(yz)

Effect on PA PA
Example: Construct the B1 symmetry-adapted linear combination of O2px orbitals for NO2

E C2 V(xz) ’V(yz)

Effect on PA PA -PB
Example: Construct the B1 symmetry-adapted linear combination of O2px orbitals for NO2

E C2 V(xz) ’V(yz)

Effect on PA PA -PB PB
Example: Construct the B1 symmetry-adapted linear combination of O2px orbitals for NO2

E C2 V(xz) ’V(yz)

Effect on PA PA -PB PB -PA

Example: Construct the B1 symmetry-adapted linear combination of O2px orbitals for NO2

E C2 V(xz) ’V(yz)

Effect on PA PA -PB PB -PA

Characters for B1
Example: Construct the B1 symmetry-adapted linear combination of O2px orbitals for NO2

E C2 V(xz) ’V(yz)

Effect on PA PA -PB PB -PA

Characters for B1 1 -1 1 -1
Example: Construct the B1 symmetry-adapted linear combination of O2px orbitals for NO2

E C2 V(xz) ’V(yz)

Effect on PA PA -PB PB -PA

Characters for B1 1 -1 1 -1

Products of rows 1 and 2

Example: Construct the B1 symmetry-adapted linear combination of O2px orbitals for NO2

E C2 V(xz) ’V(yz)

Effect on PA PA -PB PB -PA

Characters for B1 1 -1 1 -1

Products of rows 1 and 2 PA PB PB PA

The sum of the final row, divided by the order of the group (h = 4)

1
𝜓 (𝐵1 ) = 𝑝𝐴 + 𝑝𝑏
2
 Example: Construct the E symmetry-adapted linear combination of the three H1s orbitals
in NH3
Row E 𝐶3+ 𝐶3− V V V
 Example: Construct the E symmetry-adapted linear combination of the three H1s orbitals
in NH3
Row E 𝐶3+ 𝐶3− V V V

1 Effect on sA sA sB sC sA sC sB
 Example: Construct the E symmetry-adapted linear combination of the three H1s orbitals
in NH3
Row E 𝐶3+ 𝐶3− V V V

1 Effect on sA sA sB sC sA sC sB
2 Characters of E 2 -1 -1 0 0 0
 Example: Construct the E symmetry-adapted linear combination of the three H1s orbitals
in NH3
Row E 𝐶3+ 𝐶3− V V V

1 Effect on sA sA sB sC sA sC sB
2 Characters of E 2 -1 -1 0 0 0
3 Row1 x Row2 2sA -sB -sC
 Example: Construct the E symmetry-adapted linear combination of the three H1s orbitals
in NH3
Row E 𝐶3+ 𝐶3− V V V

1 Effect on sA sA sB sC sA sC sB
2 Characters of E 2 -1 -1 0 0 0
3 Row1 x Row2 2sA -sB -sC
4 Effect on sB sB sC sA sC sB sA
 Example: Construct the E symmetry-adapted linear combination of the three H1s orbitals
in NH3
Row E 𝐶3+ 𝐶3− V V V

1 Effect on sA sA sB sC sA sC sB
2 Characters of E 2 -1 -1 0 0 0
3 Row1 x Row2 2sA -sB -sC
4 Effect on sB sB sC sA sC sB sA
5 Row4 x Row2 2sB -sC -sA
 Example: Construct the E symmetry-adapted linear combination of the three H1s orbitals
in NH3
Row E 𝐶3+ 𝐶3− V V V

1 Effect on sA sA sB sC sA sC sB
2 Characters of E 2 -1 -1 0 0 0
3 Row1 x Row2 2sA -sB -sC
4 Effect on sB sB sC sA sC sB sA
5 Row4 x Row2 2sB -sC -sA
6 Effect on sC sC sA sB sB sA sC
 Example: Construct the E symmetry-adapted linear combination of the three H1s orbitals
in NH3
Row E 𝐶3+ 𝐶3− V V V

1 Effect on sA sA sB sC sA sC sB
2 Characters of E 2 -1 -1 0 0 0
3 Row1 x Row2 2sA -sB -sC
4 Effect on sB sB sC sA sC sB sA
5 Row4 x Row2 2sB -sC -sA
6 Effect on sC sC sA sB sB sA sC
7 Row4 x Row2 2sC -sA -sB
1 1 1
(2𝑆𝐴 − 𝑆𝐵 − 𝑆𝐶 ) (2𝑆𝐵 − 𝑆𝐶 − 𝑆𝐴 ) (2𝑆𝐶 − 𝑆𝐴 − 𝑆𝐵 )
6 6 6
(the three are not ‘linearly independent’)
(𝑒) 1 (𝑒) 1
𝜓1 = (2𝑆𝐴 − 𝑆𝐵 − 𝑆𝐶 ) 𝜓2 = (𝑆𝐵 − 𝑆𝐶 )
6 2
 (𝑎 ) 1 (𝑒) 1
𝜓1 1 = (𝑆𝐴 + 𝑆𝐵 + 𝑆𝐶 ) 𝜓1 = (2𝑆𝐴 − 𝑆𝐵 − 𝑆𝐶 )
3 6

(𝑒) 1
𝜓2 = (𝑆𝐵 − 𝑆𝐶 )
2