Valence shell electron pair repulsion theory

The VSEPR model predicts approximate molecular geometry by arranging the electron domains around a central chemical atom to reduce their mutual repulsion. Start with a Lewis structure, count the domains, and then distinguish the resulting electron pair geometry from the positions of the chemical atoms themselves. A lone pair counts as a domain even though it is not another chemical atom.^[ref]

Three worked counts have the same total of eight valence electrons. In methane, carbon's four plus the contributions of four hydrogen chemical atoms give $4+4=8$: four bond pairs, no lone pairs, and tetrahedral molecular geometry. In Ammonia, nitrogen's five plus three from hydrogen give $5+3=8$: three bond pairs and one lone pair, producing trigonal pyramidal molecular geometry. In water, oxygen's six plus two from hydrogen give $6+2=8$: two bond pairs and two lone pairs, producing bent molecular geometry. All three have four electron domains; their molecular geometries differ.

The regular tetrahedral directions can be represented by the unit vectorsEach pair has dot product $-1/3$, so the ideal bond angle is $\theta =\arccos (-1/3)\approx 109.47^{\circ }$. This is a geometric calculation, rather than a prediction that every four-domain molecule has that exact bond angle. Lone pairs and different kinds of chemical bonds distort the ideal arrangement; water's H–O–H angle is about $104.5^{\circ }$.^[ref]

The model is attractive because small-number bookkeeping produces a spatial prediction without first solving for every molecular orbital. Shape then helps explain chemical polarity and which hydrogen bond donor or hydrogen bond acceptor sites are accessible. It is a qualitative model, not a full calculation of the electronic energy or a universal solution for every chemical compound. Gillespie and Nyholm's 1957 review ^[ref] is a historical anchor for its development.

An electron domain is a region of electron density counted around a central chemical atom in the VSEPR model. One lone pair counts as one domain; a bond to one neighbour counts as one domain even when its bond order is two or three. Domain count is therefore different from simply counting electron pairs.

Electron pair geometry describes the arrangement of all electron domains in the VSEPR model, including lone pairs. Molecular geometry instead describes the arrangement of chemical atoms. Four domains have a tetrahedral ideal arrangement, but keeping only the bonded neighbours gives the different molecular geometries of methane, Ammonia and water.