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A valence electron belongs to the electronic arrangement used to describe a chemical atom's chemical bonds and ordinary chemical reactions. For the neutral hydrogen, carbon, nitrogen, and oxygen chemical atoms used here, the valence electrons occupy the outermost occupied electron shell. Their respective electron configurations are $1s^1$, $1s^{2}2s^{2}2p^2$, $1s^{2}2s^{2}2p^3$, and $1s^{2}2s^{2}2p^4$, giving one, four, five, and six valence electrons. See Chemistry 2e, 6.4: electron configurations and valence electrons.

Lewis structures show these valence electrons while omitting the inner electrons. Consequently, eight drawn valence electrons in water do not mean eight total electrons: neutral water has ten, with two inner oxygen electrons omitted. Neutral ammonia likewise has ten total electrons but eight valence electrons; neutral carbon dioxide has twenty-two total electrons but sixteen valence electrons.

This distinction makes the small counts useful: connections and possible lone pairs can be organized without representing every electron or solving the entire many-electron wavefunction. The outermost-electron shell shortcut applies to the examples above, rather than serving as a universal definition for all chemical elements; the electronic arrangement relevant to chemical bonds can also involve other electron subshells.

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.