Group Theory Assignment: Ammonia
(NH₃)
Course: Group Theory in Chemistry
Submitted by: Vishva S
Date: August 2025
1. Introduction
Ammonia (NH₃) is a trigonal pyramidal molecule (nitrogen at the apex, three hydrogens at
the base). It belongs to the C₃ᵥ point group. This assignment analyses its symmetry,
constructs the character table, and derives the IR-active vibrational modes. Diagrams are
hand-drawn style (black outlines, blue arrows).
2. Symmetry Elements of NH₃
The symmetry elements in NH₃ (C₃ᵥ) are:
• E — Identity operation (does nothing)
• C₃ — Threefold rotation about the principal (vertical) axis (120° and 240°)
• σᵥ — Three vertical mirror planes each containing the principal axis and a N–H bond
Figure 1: NH₃ geometry (hand-drawn style)
Figure caption: Trigonal pyramidal geometry of NH₃ (2D
projection).
Figure 2: Symmetry elements (C₃ axis and three σᵥ planes).
3. Character Table — C₃ᵥ
The character table for the C₃ᵥ point group (useful basis functions included):
Irrep E 2C₃ 3σᵥ Basis / Linear
funcs
A₁ 1 1 1 z
A₂ 1 1 -1 Rz
E 2 -1 0 (x, y)
Table 1: Character table for C₃ᵥ with common basis functions. A₁ corresponds to z
(translation along z); E to x,y translations.
4. Constructing the Reducible Representation Γ₃N
For NH₃, N = 4 atoms ⇒ 3N = 12 Cartesian degrees of freedom. We build Γ₃N by counting
the contribution to the character for each class:
• E: all 4 atoms remain fixed; each atom contributes trace 3 (x, y, z) ⇒ χ(E) = 4 × 3 = 12
• C₃ (120° about z): only the nitrogen at the top remains fixed (the three hydrogens are
permuted). The trace of a rotation by 120° in 3D about z is 1 + 2 cos 120° = 1 − 1 = 0 ⇒ χ(C₃)
=1×0=0
• σᵥ: each mirror plane leaves the nitrogen and one hydrogen unmoved (2 atoms). For an
atom on the mirror plane the Cartesian transformation has trace = 1 (z unchanged, one in-
plane coordinate changes sign) ⇒ χ(σᵥ) = 2 × 1 = 2
Therefore the characters of Γ₃N (for classes E, 2C₃, 3σᵥ) are: (12, 0, 2)
5. Reduction of Γ₃N into Irreducible Representations
Use the reduction formula: n_i = (1/h) Σ_R g_R χ_Γ(R) χ_i(R), where h=6 (order of C₃ᵥ).
Irrep characters: A₁:(1,1,1), A₂:(1,1,−1), E:(2,−1,0). Compute inner products:
⟨Γ₃N, A₁⟩ = (1/6)[1·12·1 + 2·0·1 + 3·2·1] = (1/6)(12 + 0 + 6) = 3 ⇒ 3A₁
⟨Γ₃N, A₂⟩ = (1/6)[1·12·1 + 2·0·1 + 3·2·(−1)] = (1/6)(12 + 0 − 6) = 1 ⇒ 1A₂
⟨Γ₃N, E ⟩ = (1/6)[1·12·2 + 2·0·(−1) + 3·2·0] = (1/6)(24 + 0 + 0) = 4 ⇒ 4E
Therefore: Γ₃N = 3A₁ ⊕ A₂ ⊕ 4E
6. Vibrational Representation Γ_vib
Translations correspond to A₁ + E. Rotations correspond to A₂ + E. Hence:
Γ_trans+rot = (A₁ + E) + (A₂ + E) = A₁ + A₂ + 2E
Γ_vib = Γ₃N − (Γ_trans+rot) = (3A₁ ⊕ A₂ ⊕ 4E) − (A₁ ⊕ A₂ ⊕ 2E) = 2A₁ ⊕ 2E
So NH₃ has 2A₁ + 2E vibrational modes (total 6 modes, since E is doubly degenerate ⇒ 2×2 +
2×1 = 6).
7. IR Activity
A vibrational mode is IR-active if it transforms as x, y, or z (components of the dipole
moment). From the character table:
• A₁ transforms as z ⇒ IR active (z-polarized)
• E transforms as (x, y) ⇒ IR active (x/y-polarized)
• A₂ has no x,y,z basis ⇒ IR inactive
Therefore all vibrational modes in NH₃ (2A₁ and 2E) are IR-active.
8. Vibrational Modes — Diagrams (hand-drawn style)
Figure: A₁ — Symmetric N–H stretch (ν₁). All H atoms move radially
in/out along N–H bonds; N moves slightly opposite. IR active along z.
Figure: A₁ — Umbrella/inversion mode (ν₂). Hydrogens move
up/down relative to N (inversion). IR active along z.
Figure: E — Asymmetric stretch (ν₃), component 1. One H moves
opposite to the other two (degenerate pair). IR active in x/y.
Figure: E — Asymmetric stretch (ν₃), component 2 (orthogonal
partner).
Figure: E — Degenerate bends (ν₄), component 1 (in-plane
scissoring). IR active in x/y.
Figure: E — Degenerate bends (ν₄), component 2 (orthogonal
partner).
9. Conclusion
Using group theory and the C₃ᵥ character table, we find NH₃ has 6 vibrational modes
classified as 2A₁ + 2E. Both A₁ and E modes are IR-active because they transform like z and
(x,y) respectively. Diagrams above are hand-drawn style (black outlines and blue arrows) to
match a notebook sketch appearance.
