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In bent molecular geometry, two neighbours and their central chemical atom form a noncollinear triangle, with an interior bond angle strictly between $0^{\circ }$ and $180^{\circ }$. Water, ${\mathrm{H}}_2\mathrm{O}$, is the standard example. The NIST CCCBDB experimental water entry, internal coordinates, citing Hoy and Bunker (1979) gives the equilibrium H–O–H bond angle as $104.4776^{\circ }$ with quoted uncertainty $0.0019^{\circ }$, usually rounded to $104.5^{\circ }$.

The oxygen in water has two bonding electron domains and two lone pairs. Its ideal electron pair geometry is tetrahedral, while the three atomic nuclei give bent molecular geometry. Three points always lie in a plane; this does not make the four-domain scaffold planar. Nor does the word bent by itself determine an electron domain count: the same atomic shape can arise from other domain arrangements.

In an illustrative model with two equal bond-dipole contributions of magnitude $p$ separated by bond angle $\theta$, their sum of vectors points along the bisector and has magnitude $2p\cos (\theta /2)$. At $180^{\circ }$ it vanishes; at $104.4776^{\circ }$ it is approximately $1.2247p$. This ratio is a geometric calculation, not a prediction of water's measured electric dipole moment. The entire electron density, including contributions represented by lone pairs, matters. Water is a polar molecule; chemical polarity helps explain its interactions with other polar molecules. See McMurry, Organic Chemistry, §2.2: water, lone-pair contributions, and polarity.

Chemical polarity concerns unequal distribution of electron density in a chemical bond or molecule. A polar molecule has a permanent electric dipole moment; the effects of individual bonds must be combined with their spatial arrangement. In a symmetric linear carbon dioxide molecule, opposing bond-dipole contributions cancel. In water, its bent molecular geometry prevents that cancellation, giving a permanent electric dipole moment.^[ref]

A finite electric dipole consists of equal and opposite electric charges separated by a nonzero displacement. It has charge neutrality but a nonzero electric dipole moment $\mathbf{p}=q\mathbf{d}$. An ideal point electric dipole is the mathematical limit $d=|\mathbf{d}|\to 0$ with $\mathbf{p}$ fixed, so $q$ must increase as $1/d$. Shrinking the separation while holding $q$ fixed instead makes the electric dipole moment vanish. The ideal electric dipole describes an exterior electric field; it does not reproduce the two near-charge singularities or the internal structure of a molecule. ^[ref].

Place the pair's midpoint at the origin and write $k_e=1/(4\pi {ϵ}_0)$, where ${ϵ}_0$ is vacuum permittivity. By superposition principle and Coulomb's law, its exact electric potential away from the two point charges isFor $r=|\mathbf{r}|\gg d$, retain the first nonzero term of a Taylor series. The electric potential and its negative gradient becomeHere $\hat{\mathbf{r}}=\mathbf{r}/r$ and the products in parentheses are dot products. These are exact exterior formulas for the ideal electric dipole and distant approximations for a finite pair. The electric field on the outer axis points along $\mathbf{p}$ with magnitude $2k_{e}p/r^3$; on the perpendicular bisector it points opposite $\mathbf{p}$ with magnitude $k_{e}p/r^3$. This directional structure is what a scalar total electric charge misses. ^[ref].

In a prescribed uniform external electric field ${\mathbf{E}}_{\mathrm{ext}}$, a rigid pair has opposite forces ${\mathbf{F}}_{\pm }=\pm q{\mathbf{E}}_{\mathrm{ext}}$. Its net force is zero, but summing their moments about the midpoint gives the torqueThe cross product makes the torque perpendicular to both the electric dipole moment and the external electric field. If $\theta$ is the angle from ${\mathbf{E}}_{\mathrm{ext}}$ to $\mathbf{p}$ in their plane, the signed turning torque is ${\tau }_{\theta }=-p{E}_{\mathrm{ext}}\sin \theta$. It tends to reduce a small positive $\theta$. ^[ref].

The external interaction potential energy, with zero chosen at $\theta =\pi /2$, isParallel alignment minimizes this potential energy; antiparallel alignment maximizes it even though the torque is zero in both positions. This omits the pair's constant internal binding potential energy and assumes a fixed permanent electric dipole moment. ^[ref].

A nonuniform external electric field can exert a net force on a neutral electric dipole. Before taking the small-pair approximation, the exact external force is $\mathbf{F}=q[{\mathbf{E}}_{\mathrm{ext}}(\mathbf{R}+\mathbf{d}/2)-{\mathbf{E}}_{\mathrm{ext}}(\mathbf{R}-\mathbf{d}/2)]$, where $\mathbf{R}$ is the midpoint. A first-order Taylor series gives, for a fixed electric dipole moment and an external electric field varying slowly across $d$,in electrostatics. The last equality uses the vanishing curl of the external electric field, with $\mathbf{p}$ held fixed while differentiating. Thus uniform external electric fields turn a misaligned electric dipole, whereas gradients can also move its midpoint. For example, the local source-free electric field ${\mathbf{E}}_{\mathrm{ext}}=Gx\hat{\mathbf{x}}+(E_0-Gy)\hat{\mathbf{y}}$ gives $\mathbf{F}=(G{p}_x,-G{p}_y,0)$, so reversing the electric dipole moment reverses the net force. This stipulated local model has zero divergence and zero curl.

A motivating experiment is Filsinger and colleagues' study of electrostatic deflection of polar molecules. Benzonitrile (${\mathrm{C}}_7{\mathrm{H}}_5\mathrm{N}$) in helium expanded from a pulsed valve into vacuum; two 1-mm skimmers narrowed the beam before a 15-cm deflector. A grounded trough and a high-voltage rod produced a vertical electric field gradient. Scanning a focused laser vertically downstream and recording benzonitrile ions from photoionization measured the beam's relative density. With voltage off, the profile spanned about 2 mm; applying voltage shifted and broadened it upwards. At 10 kV, many molecules lay outside the original profile. ^[ref].

Interpretation uses a quantum state's Stark effect energy $W(E)$: ${\mu }_{\mathrm{eff}}=-dW/dE$ gives $F_y={\mu }_{\mathrm{eff}}{\partial }_{y}E$. States whose energy falls with increasing electric field seek stronger fields. The voltage-off profile controls the mechanical aperture. Inferring state populations needs calculated trajectories, speed distributions and a rotational temperature model; profile displacement alone does not measure a permanent electric dipole moment uniquely. This is an electric Stark effect experiment, with photoionization occurring after deflection. ^[ref].

For the symmetric finite pair, the first omitted electric multipole expansion term after the electric dipole is third order, so typical relative errors scale as $(d/r{)}^2$. This stronger error estimate need not hold for an arbitrary neutral molecule with a nonzero electric quadrupole moment. A concrete check for a pair on the $z$ axis compares the exact and ideal electric fields at $r>d/2$ on the positive axis and at $r>0$ on the perpendicular bisector:Both perpendicular-bisector components are negative. At $r=5d$, the ratios are approximately $1.0203$ and $0.9852$: errors of $+2.03\%$ and $-1.48\%$ relative to the ideal electric field. The condition $r\gg d$ concerns observing the pair's own electric field; the separate condition for its external force approximation concerns variation of the applied electric field across the pair.

The electric dipole moment measures the first spatial moment of signed electric charge. For localized point charges $q_i$ at positions ${\mathbf{r}}_i$, or an integrable charge density $\rho (\mathbf{r})$ with a finite first moment, define^[ref].

The electric dipole moment is a vector with SI units $\mathrm{C}\mathrm{m}$: coulombs times length in metres. Opposite electric charges can cancel in $Q$ while contributing in the same direction to $\mathbf{p}$. For a neutral pair with positive electric charge $q>0$ at ${\mathbf{r}}_{+}$ and negative electric charge $-q$ at ${\mathbf{r}}_{-}$,Thus the electric dipole moment points from negative to positive electric charge, not along the attraction between the two point charges. ^[ref].

Changing the coordinate origin changes the position vectors, not the physical electric charge distribution. If the new origin is at $\mathbf{a}$ relative to the old origin, ${\mathbf{r}}_i^{\prime }={\mathbf{r}}_i-\mathbf{a}$, so direct substitution givesConsequently charge neutrality makes the electric dipole moment independent of the origin. For a system with nonzero total electric charge, always specify the origin: a single point charge at the old origin has $\mathbf{p}=0$ but ${\mathbf{p}}^{\prime }=-Q\mathbf{a}$. This is coordinate bookkeeping, not a newly created electric dipole. The full electric potential stays the same at the same physical point; the terms of its electric multipole expansion and the observation coordinates change together.

As a stipulated numerical example, put $+2\mathrm{nC}$ at $(1,0,0)\mathrm{mm}$ and $-2\mathrm{nC}$ at $(-1,0,0)\mathrm{mm}$. Their total electric charge is zero and $\mathbf{p}=(4\times 10^{-12},0,0)\mathrm{C}\mathrm{m}$. Translating the origin by $(3,-2,0)\mathrm{mm}$ leaves this electric dipole moment unchanged. Adding $+1\mathrm{nC}$ at the old origin instead gives $Q=1\mathrm{nC}$ and ${\mathbf{p}}^{\prime }=(1,2,0)\times 10^{-12}\mathrm{C}\mathrm{m}$. Distinguishing these two cases prevents the mistaken claim that every electric dipole moment is independent of the origin.

The usefulness of the electric dipole moment is compression: many internal electric charges determine one vector governing the leading distant electric potential of a neutral localized object when $\mathbf{p}\ne 0$. ^[ref]. A polar molecule need not literally contain two point charges; its atomic nuclei and electron density collectively give an electric dipole moment. For example, the chemical polarity of water reflects its bent molecular geometry, whereas the symmetric linear molecular geometry of carbon dioxide makes its permanent electric dipole moment vanish. ^[ref]. A collection of such electric dipole moments per unit volume gives electric polarization. ^[ref].

Two routes to electric polarization are displacement and reorientation. An electric field can shift the centres of positive and negative electric charge in a neutral chemical atom or molecule, inducing an electric dipole moment. A polar molecule already has an electric dipole moment; a field biases its orientation. At finite temperature, random molecular motion opposes complete alignment, so a nonzero average need not mean that every electric dipole points the same way.^[ref]

For a single species with number per unit volume $n$, the electric polarization isThe brackets denote the local average electric dipole moment, rather than its magnitude. Opposite orientations can cancel while individual electric dipole moments remain nonzero.^[ref] This averaging explains how an initially unpolarized material can respond strongly without acquiring net electric charge.

A molecule, using the International Union of Pure and Applied Chemistry (IUPAC) convention, is an electrically neutral entity containing two or more chemical atoms. Its constituents form a bound unit through chemical bonds; merely drawing a boundary around neighboring particles does not make a molecule. The neutrality requirement concerns total electric charge, not the absence of internal charge separation: water is a polar molecule with zero total electric charge.^[ref]

One water molecule, ${\mathrm{H}}_2\mathrm{O}$, contains two hydrogen and one oxygen chemical atom. One molecular oxygen molecule, ${\mathrm{O}}_2$, contains two oxygen chemical atoms; a molecule need not contain different chemical elements. One carbon dioxide molecule, $\mathrm{C}{\mathrm{O}}_2$, contains one carbon and two oxygen chemical atoms. The molecular formula records these inventories, while molecular geometry describes their arrangement. Water and carbon dioxide are chemical compounds; molecular oxygen is a form of one chemical element.

Ordinary crystalline sodium chloride, $\mathrm{NaCl}$, contains an extended arrangement of sodium cations $\mathrm{N}{\mathrm{a}}^{+}$ and chlorine anions $\mathrm{C}{\mathrm{l}}^{-}$. Its formula unit specifies one of each for compositional accounting, without selecting a unique isolated pair. Bulk neutrality therefore does not imply a material consists of neutral molecules. This statement concerns the ionic crystal; the physical state and conditions matter when deciding what particles a chemical formula represents.^[ref]

A polyatomic ion is a charged bound group of chemical atoms, such as hydronium, ${\mathrm{H}}_3{\mathrm{O}}^{+}$. A molecular ion formed by removing an electron from intact water, ${\mathrm{H}}_2{\mathrm{O}}^{\bullet +}$, retains the same atom inventory but has net electric charge $+e$. Neither satisfies the neutral-molecule definition. Distinguishing these entities makes molecular count and amount of substance and mass spectrometry interpretable: say whether the count is of chemical atoms, neutral molecules, ions, or formula units.

The useful surprise is that a molecule can be treated as one particle for motion and counting while retaining internal structure. Its molar mass connects a particle inventory to bulk mass; molecular rotation and molecular vibration reveal internal organization. The continuum approximation uses bulk fields in place of individual molecular positions and motions.

A polar covalent bond shares electrons unequally, as in hydrogen chloride.

The word “polar” qualifies the sharing within a covalent bond; it does not require complete transfer of an electron or an isolated cation–anion pair. In $A^{\delta +}-B^{\delta -}$, the signs identify the relatively electron-poor and electron-rich ends, while $\delta$ leaves the amount unspecified. A neutral Lewis structure can give both chemical atoms zero formal charge and still correspond to a polar covalent bond: equal division of the bond pair is a formal allocation, whereas bond polarization concerns the actual electron density.

Local and molecular descriptions answer different questions. Calling one chemical bond a polar covalent bond does not establish that the whole molecule is a polar molecule. Combine the bond dipoles with the molecular geometry, then check for molecular dipole cancellation. This lets a short electronegativity comparison explain a local tendency without confusing it with the observable electric dipole moment of the whole molecule.

A polar molecule has a nonzero permanent electric dipole moment because of its internal electric charge distribution. It can still have zero total electric charge. Water is polar; a nonpolar molecule has no permanent electric dipole moment.

In trigonal pyramidal molecular geometry, three neighbouring chemical atoms form a triangular base and the central chemical atom lies outside its plane. The pyramid has four atomic nuclei; its central chemical atom is the apex, not the centre of the base. Ammonia, ${\mathrm{NH}}_3$, has this arrangement. The ^[ref] lists an H–N–H bond angle of $106.67^{\circ }$, commonly rounded to $106.7^{\circ }$ or about $107^{\circ }$.

The Lewis structure of Ammonia allocates eight valence electrons as three bond pairs and one lone pair. Four electron domains therefore suggest tetrahedral electron pair geometry; removing the lone pair marker leaves three hydrogen chemical atoms below nitrogen. The VSEPR model treats the lone pair as more space-demanding and predicts compression relative to $109.4712^{\circ }$, but it does not calculate the precise $106.67^{\circ }$ value. See Chemistry 2e, §7.6: lone-pair effects.

Three equal bond-dipole contributions in this pyramid cancel sideways, but retain a component along its axis. By contrast, three equal contributions lying in one plane at $120^{\circ }$ would cancel completely. This shows how a small change in molecular geometry can permit a permanent electric dipole moment. Ammonia is a polar molecule; NIST lists a measured magnitude of about $1.476$ debye in the same ^[ref]. The vector argument predicts allowed direction and cancellation, not the full measured magnitude.