VSEPR Theory

Valence Shell Electron Pair Repulsion Theory

VSEPR Principle

Core Concept: Electron pairs around a central atom repel each other and arrange themselves to minimize repulsion, achieving maximum distance from each other.

1. Draw Lewis Structure

Determine total valence electrons and draw bonds

2. Count Electron Domains

• Bonding domains: Single, double, or triple bonds (each counts as ONE)
• Lone pairs: Non-bonding electron pairs

3. Determine Electron Geometry

Based on total number of electron domains

4. Determine Molecular Geometry

Based on bonding domains only (ignore lone pairs for shape name)

Electron Domain Geometries

2 Electron Domains

Electron Geometry: Linear

Bond Angle: 180°

Example: BeCl₂, CO₂

4 Electron Domains

Electron Geometry: Tetrahedral

Bond Angle: 109.5°

Example: CH₄, NH₄⁺

5 Electron Domains

Electron Geometry: Trigonal Bipyramidal

Bond Angles: 90°, 120°, 180°

Example: PCl₅, AsF₅

6 Electron Domains

Electron Geometry: Octahedral

Bond Angle: 90°, 180°

Example: SF₆, PF₆⁻

Molecular Geometries with Lone Pairs

DomainsBondingLone PairsMolecular ShapeBond AngleExample
220Linear180°CO₂
330Trigonal Planar120°BF₃
321Bent<120°SO₂
440Tetrahedral109.5°CH₄
431Trigonal Pyramidal~107°NH₃
422Bent~104.5°H₂O
550Trigonal Bipyramidal90°, 120°PCl₅
541See-Saw<120°, <90°SF₄
532T-Shaped<90°ClF₃
523Linear180°XeF₂
660Octahedral90°SF₆
651Square Pyramidal<90°BrF₅
642Square Planar90°XeF₄

Bond Angle Modifications

Lone Pair Repulsion

Repulsion Strength: LP-LP > LP-BP > BP-BP

Lone pairs occupy more space than bonding pairs, compressing bond angles

CH₄: 109.5° (no LP)
NH₃: 107° (1 LP)
H₂O: 104.5° (2 LP)

Multiple Bonds

Double and triple bonds contain more electron density, slightly repel other bonds more

H₂CO (formaldehyde): H-C-H angle < 120°

Electronegativity Effects

More electronegative substituents attract bonding electrons, slightly reducing bond angles

Worked Examples

Example 1: H₂O (Water)

Step 1: Draw Lewis structure

O has 6 valence e⁻, each H has 1 → total = 8 e⁻

Step 2: Count electron domains around O

2 bonding domains (O-H bonds)

2 lone pairs

Total = 4 electron domains

Step 3: Electron geometry

Tetrahedral

Step 4: Molecular geometry (2 bonds, 2 LP)

Bent, ~104.5°

Example 2: SF₄ (Sulfur Tetrafluoride)

Step 1: Lewis structure

S has 6 valence e⁻, each F has 7 → S forms 4 bonds, 1 LP remains

Step 2: Count electron domains

4 bonding domains (S-F bonds)

1 lone pair

Total = 5 electron domains

Step 3: Electron geometry

Trigonal Bipyramidal

Step 4: Lone pair placement

Lone pairs prefer equatorial positions (less repulsion)

Step 5: Molecular geometry (4 bonds, 1 LP)

See-Saw shape

Example 3: XeF₄ (Xenon Tetrafluoride)

Step 1: Lewis structure

Xe has 8 valence e⁻, forms 4 bonds, 2 LP remain

Step 2: Count electron domains

4 bonding domains

2 lone pairs

Total = 6 electron domains

Step 3: Electron geometry

Octahedral

Step 4: Lone pair placement

2 LP occupy opposite positions (trans)

Step 5: Molecular geometry (4 bonds, 2 LP)

Square Planar, 90°

Common Mistakes

⚠️

Forgetting Lone Pairs

Always count ALL electron domains, not just bonds!

⚠️

Multiple Bonds = Multiple Domains

Double and triple bonds count as ONE electron domain!

⚠️

Confusing Electron vs Molecular Geometry

Electron geometry uses all domains; molecular shape ignores LP positions!