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🔷 COVALENT BONDING & VSEPR 🔷

Electron-pair geometry · Molecular shape · AXₙEₘ notation · Bond angles
CHEMSIM v1.0

⚡ INTERACTIVE SIMULATION

🔷 3D Geometry
⚡ Electron Domains
🌀 Lone-Pair Distortion
↗ Dipole Moments
⚖ Compare Shapes
Bond Angles
Dipole Vector
Repulsion Strength
VSEPR Lookup Table
MOLECULAR GEOMETRY
Tetrahedral
BOND ANGLE
109.5°
ELECTRON DOMAINS
4
LONE PAIRS
0
HYBRIDIZATION
sp³
VSEPR NOTATION
AX₄
Preset Molecule
Bonded atoms (X)4
Lone pairs (E)0
Bond length (pm)109
Lone-pair repulsion factor1.20
Auto-rotate speed1.0×
Show atom labels
Show lone pairs
Show bond angles
Show dipole vectors
Show electron repulsion

💡 THE IDEA, STEP BY STEP

Blow up a few long balloons and tie them together at their necks. They don't pile on top of each other — they swing apart until they're spread as evenly as possible around the knot. The groups of electrons around an atom do exactly the same thing. They're all negatively charged, so they repel, and they settle into whatever arrangement keeps them as far apart as they can get. That arrangement is the shape of the molecule. That single idea is the whole of VSEPR — Valence-Shell Electron-Pair Repulsion.

Counting the groups

Look at the central atom and count two things: the number of atoms bonded to it, $N_X$, and the number of lone pairs sitting on it, $N_E$. Add them to get the steric number,

$$ \text{SN} = N_X + N_E $$

— the number of electron "groups" that have to share the space. Each value of SN has exactly one most-spread-out answer: 2 groups go to opposite sides ($180°$, linear); 3 groups make a flat triangle ($120°$); 4 groups point to the corners of a tetrahedron ($109.5°$). Methane, CH₄, has 4 bonds and no lone pairs, so $\text{SN}=4$ and its four H atoms sit at $109.5°$ — the classic tetrahedron.

Why lone pairs bend the picture

A double or triple bond still counts as just one group, because all of its electrons point the same way — that's why CO₂ ($\text{SN}=2$) is linear, not bent. A lone pair counts as a group too, but it spreads over a wider angle than a bond, because no second nucleus is pulling it in. So lone pairs push the bonds harder than bonds push each other:

$$ k_{\text{lp-lp}} > k_{\text{lp-bp}} > k_{\text{bp-bp}} $$

Start from the tetrahedral $109.5°$, swap one bond for a lone pair and ammonia (NH₃) drops to $107°$; swap two and water (H₂O) closes to $104.5°$. In the sim above, the X and E sliders set $N_X$ and $N_E$, and the lone-pair repulsion factor sets how much harder those lone pairs shove.

Try this in the sim above

① Set X = 4, E = 0 (methane) and read $109.5°$; now raise E to 1, then 2, and watch the bond angle fall toward ammonia and then water. ② With water loaded, drag the lone-pair repulsion factor upward and watch the H–O–H angle compress even further. ③ Switch to the Dipole Moments view and compare CO₂ (symmetric — the bond arrows cancel, $\mu=0$) with H₂O (bent — the arrows add up to a net $1.85$ D, which is why water is such a good solvent).

📐 EQUATION DERIVATION

VSEPR — Steric Number, Electron-Domain Repulsion & Bond-Angle Prediction
$$ \text{SN} = N_X + N_E,\qquad U_{\text{rep}} = \sum_{i

The Valence Shell Electron Pair Repulsion (VSEPR) theory of Gillespie & Nyholm (1957) states that the geometry around a central atom is dictated by the requirement that bonded atoms (X) and lone pairs (E) arrange themselves to minimise mutual electrostatic and Pauli repulsion. The arrangement that minimises this repulsion is determined by the steric number $\text{SN} = N_X + N_E$.

Symbol Definitions

SymbolMeaningUnit / Range
$\text{SN}$Steric number = total electron domains2–7 (integer)
$N_X$Number of bonded atoms (σ-bonds)integer
$N_E$Number of lone pairs on central atominteger
$\theta_{ij}$Angle between domains $i$ and $j$ at the centredegrees
$r_{ij}$Inter-domain distance on a unit sphere = $2\sin(\theta_{ij}/2)$dimensionless
$k_{ij}$Repulsion weight: lp–lp > lp–bp > bp–bpdimensionless
$p$Repulsion exponent (typically 6–12 for Pauli core)dimensionless
$\mu$Dipole moment of moleculeD (Debye) = 3.336×10⁻³⁰ C·m

Step-by-Step Derivation

STEP 1 — Place all electron domains on a unit sphere
Each electron domain (a bond, double bond, triple bond, or lone pair counts as one domain) is represented by a point on a sphere centred at the nucleus. For SN = $n$, we want $n$ points whose mutual repulsion is minimised.
STEP 2 — Define a repulsion energy
Approximating the closed-shell Pauli repulsion as a power-law, $$ U_{\text{rep}} = \sum_{i
STEP 3 — Minimise to find ideal geometry
Setting $\partial U_{\text{rep}}/\partial \theta_{ij} = 0$ subject to spherical constraints yields the platonic-symmetry solutions: $$ \begin{array}{lcl} \text{SN}=2 & \to & \theta=180° \text{ (linear)} \\ \text{SN}=3 & \to & \theta=120° \text{ (trigonal planar)} \\ \text{SN}=4 & \to & \theta=109.47° \text{ (tetrahedral)} \\ \text{SN}=5 & \to & 90°/120° \text{ (trig. bipyramidal)} \\ \text{SN}=6 & \to & 90° \text{ (octahedral)} \\ \text{SN}=7 & \to & \text{pentagonal bipyramidal} \end{array} $$
STEP 4 — Tetrahedral angle from geometry
The tetrahedral angle is exactly derivable. Place 4 vertices at $(1,1,1),(1,-1,-1),(-1,1,-1),(-1,-1,1)$. The angle between any two vectors from origin is: $$ \cos\theta = \frac{\vec a\cdot\vec b}{|\vec a||\vec b|} = \frac{1-1-1}{3} = -\tfrac{1}{3} $$ $$ \theta = \arccos(-1/3) = 109.4712°\ldots $$
STEP 5 — Lone pairs distort ideal angles
Lone pairs occupy more angular volume than bond pairs (no second nucleus to localise them). Setting $k_{\text{lp-lp}} > k_{\text{lp-bp}} > k_{\text{bp-bp}}$ (roughly $1.4:1.2:1.0$) and re-minimising shrinks bond–bond angles. Result for tetrahedral parents: $$ \text{CH}_4: 109.5°,\quad \text{NH}_3: 107.0°,\quad \text{H}_2\text{O}: 104.5° $$
STEP 6 — Net molecular dipole from vector sum
Each polar bond contributes a dipole vector $\vec\mu_i$. The molecular dipole is the vector sum: $$ \vec\mu_{\text{mol}} = \sum_i \vec\mu_i $$ In symmetric AX$_n$ molecules (CO₂, BF₃, CH₄, SF₆), bond dipoles cancel: $\vec\mu_{\text{mol}}=0$. Asymmetric (H₂O, NH₃, NH₃, ClF₃): they add to a non-zero net dipole.

Mapping to Simulation

  • X slider → $N_X$ — number of σ-bonded atoms
  • E slider → $N_E$ — number of lone pairs (changes molecular shape from electron-domain shape)
  • Lone-pair repulsion factor → ratio $k_{\text{lp-bp}}/k_{\text{bp-bp}}$ — higher value compresses bond–bond angles further
  • Bond length → length of M–X bond in pm; only affects dipole magnitude
  • Preset → loads a known molecule with experimentally observed geometry and angles

Worked Example — H₂O

For H₂O: $N_X=2$, $N_E=2$, $\text{SN}=4$ → tetrahedral electron geometry, but bent molecular shape because we only "see" the two H atoms. With an idealised tetrahedral angle of 109.5° and the lp–bp repulsion factor pushing the H atoms together:

$$ \theta_{\text{HOH}} = 109.5° - \Delta_{\text{lp}} \approx 104.5°,\quad \mu_{\text{H}_2\text{O}}\approx 1.85\text{ D} $$

The 5° distortion from the ideal tetrahedral angle is exactly what gives water its bent shape, polarity, hydrogen bonding, and ultimately makes life possible.

📚 Reference: Gillespie, R. J. & Nyholm, R. S. — Quart. Rev. Chem. Soc. 11, 339 (1957); Housecroft & Sharpe — Inorganic Chemistry, 5th Ed., Chapter 2.8: "VSEPR theory"; Atkins & de Paula — Physical Chemistry, 11th Ed., Section 9D.3: "VSEPR model".

❓ FREQUENTLY ASKED QUESTIONS

📚 Recommended Resource: LibreTexts Chemistry — "VSEPR Theory" (chem.libretexts.org); Chemguide.co.uk — Jim Clark's "Shapes of Molecules and Ions" series; MIT OCW 5.111 Lecture Notes on VSEPR.

⚠️ COMMON MISCONCEPTIONS

📚 Reference: Furió, C. & Calatayud, M. L. — J. Chem. Educ. 73, 36 (1996), "Difficulties with the geometry and polarity of molecules"; Taber, K. S. — Chemical Misconceptions: Prevention, Diagnosis and Cure, RSC, 2002, Vol. II, Ch. 3: "Covalent Bonding"; Peterson, R. F. & Treagust, D. F. — Res. Sci. Educ. 19, 233 (1989).