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Like-charged colloids can resist aggregation because bringing their electric double layers together costs free energy. In DLVO theory, screened electrostatic repulsion competes with attractive Van der Waals forces. A repulsive barrier much larger than $k_{B}T$ suppresses thermally activated aggregation, although the dispersion can remain metastable. Lower ionic strength generally lengthens the Debye–Hückel screening length, while multivalent counterions or added salt shorten it and can lower the barrier. The surface charge, charge regulation and solvent-dependent attraction also matter; screening length alone does not guarantee stability.

DLVO theory combines screened electrostatic repulsion from overlapping electric double layers with attractive Van der Waals forces to model colloid stability. A repulsive barrier can inhibit aggregation even when a deep short-distance attractive minimum exists. Increasing electrolyte concentration reduces the screening length and can lower that barrier. Molecular surface forces and polymer-mediated interactions require additions to this description.

Molecular orbital theory describes the electronic arrangement of a molecule using molecular orbitals: one-electron spatial wavefunctions extending over the combined atomic nuclei. Filling bonding molecular orbitals can stabilize a chemical bond; filling antibonding molecular orbitals opposes that stabilization. A molecular orbital is a building block of a many-electron description, rather than the entire many-electron wavefunction. See Robert W. Field, MIT 5.61, lecture 24, pp. 1–4: molecular orbitals and the LCAO approximation.

First make the interference visible with an exactly normalized one-dimensional toy. Replace the three-dimensional $1s$ atomic orbitals of the hydrogen atom by two Gaussian functions centred at $x=\pm a$, with dimensionless $x$ and $a>0$:The normalized sum and difference are ${\psi }_{\pm }=({\varphi }_A\pm {\varphi }_B)/\sqrt{2(1\pm S)}$, following the same linear combination of atomic orbitals algebra. At $a=1$, the orbital overlap is $S=e^{-1}\approx 0.367879$. At the midpoint, ${\varphi }_A(0)={\varphi }_B(0)\approx 0.455581$, givingBoth probability densities have total integral one: interference redistributes probability, rather than creating an extra electron. These are toy wavefunctions, not actual hydrogen atom orbitals or predictions of molecular hydrogen energies.

Now fill the two $1s$-derived molecular orbitals in the minimal model. The lower bonding molecular orbital is labelled ${\sigma }_g$; the upper antibonding molecular orbital is ${\sigma }_u^{\ast }$. The Pauli exclusion principle permits at most two electrons in each spatial molecular orbital, with opposite spin projections along a chosen axis. For the lowest electron configuration in this model, fill ${\sigma }_g$ first. The subscripts $g$ and $u$ denote even and odd behaviour under inversion through the midpoint; the star marks an antibonding molecular orbital. See Flowers et al., Chemistry 2e, 8.4: occupancy and bond order and Field, MIT 5.61, lecture 25, pp. 1–3: bonding, antibonding, and symmetry labels.

With $N_b$ electrons in bonding molecular orbitals and $N_a$ in antibonding molecular orbitals, the model's bond order is $b=(N_b-N_a)/2$. The three elementary counts are:

The zero bond order says this minimal model gives no net covalent bond for ${\mathrm{He}}_2$. It does not rule out every bound pair of helium chemical atoms: a very weak Van der Waals force can bind a neutral helium dimer, which has been observed experimentally. See Zeller et al., Imaging the He2 quantum halo state using a free electron laser, PNAS 113, 14651–14655 (2016), p. 14651: van der Waals binding and Luo et al., The weakest bond: Experimental observation of helium dimer, Journal of Chemical Physics 98, 3564–3567 (1993). The bond order count does not include that weak binding mechanism.

The useful surprise is that sharing alone does not determine a chemical bond: the relative quantum phase and the occupancy matter together. The same two shapes explain why adding an electron to a bonding molecular orbital increases the model's bond order, while adding one to an antibonding molecular orbital decreases it. Molecular orbital theory also accounts for the unpaired electrons and paramagnetism of molecular oxygen, which its all-paired Lewis structure misses. See Chemistry 2e, 8.4: the molecular orbital description of oxygen.

For two equal spheres of radius $a$ separated by a surface gap $h\ll a$, a positive Hamaker constant $A_H$ gives the nonretarded Van der Waals force approximation $U=-A_{H}a/(12h)$ and $F=-dU/dh=-A_{H}a/(12h^2)$. The Derjaguin approximation derives the geometry factor from the planar interaction energy per area $W=-A_H/(12\pi h^2)$ and effective radius $a/2$. A sphere and plane instead have effective radius $a$, doubling the force at the same gap. Molecular repulsion, roughness and retardation limit these continuum formulas.

A paratope is the recognizing surface on an antibody; the epitope is the recognized feature on its antigen. Contacts depend on spatial arrangement and chemistry, including hydrogen bonds and Van der Waals forces. Thus a paratope is not simply a slot for a protein primary structure string. A folded protein can bring distant amino acid residues into one epitope. ^[ref]

Each thiocyanate is a three-metal bridge, ${\mu }_3$-$\kappa N:\kappa S:\kappa S$: its nitrogen donates to one metal and its sulfur donates to two other metals. Thus the coordination ligand is ambidentate, but the structure uses both ends and shares the sulfur donor. Each metal receives two nitrogen and four sulfur donors, giving an approximately octahedral $\mathrm{M}{\mathrm{N}}_2{\mathrm{S}}_4$ coordination sphere. Six donor contacts per metal are consistent with two coordination ligands per metal because each coordination ligand contributes three contacts across the lattice. Sharing these contacts produces a coordination polymer within each layer; the interlayer Van der Waals force does not add coordination bonds. The index ${\mu }_3$ counts metal centres, whereas a hapticity label would count adjacent coordinated coordination ligand atoms and would not describe this connectivity correctly.^[ref]

For the same geometry, separation and intervening medium, the attractive Van der Waals force scales with the effective Hamaker constant. With the constants treated as applying to those same conditions,The silver particles attract more strongly. This comparison is conditional on a common geometry and on using the appropriate constants across the actual medium. Constants for particles in vacuum cannot automatically be applied unchanged across a solvent.

A stable charge-stabilized dispersion has an interaction barrier large compared with $k_{B}T$. In DLVO theory, the total pair potential combines attractive Van der Waals forces with repulsion from overlapping electric double layers. Similar surface charges raise the free energy of overlap; a sufficiently high positive barrier prevents thermally diffusing particles from reaching the deep primary minimum near contact.

Other stabilization mechanisms include steric stabilization by solvated surface chains and combined electrosteric protection by charged chains. Such contributions are additional to the simplest DLVO pair potential. Increasing salt shortens the Debye length, so double-layer repulsion becomes shorter-ranged and the protective barrier can decrease.

Take an attractive nonretarded molecular potential $U(R)=-\beta /R^6$, with molecular number densities $n_1,n_2$. Its force magnitude is $6\beta /R^7$. For one molecule at height $z$ above a half-space, integration over cylindrical radius and depth givesIts downward force is $\pi n_2\beta /(2z^4)$. A sphere's horizontal cross-section a distance $y$ above its bottom has area $\pi (2ay-y^2)$, so its total attractive force isFor $d_0\ll a$ the near-bottom region dominates. Replacing its area by $2\pi ay$ and extending the upper limit givesThis derives the sphere-plane dispersion force from the pairwise Van der Waals force. Hereafter $A>0$ denotes the magnitude of the effective repulsive interaction across water, rather than the signed attractive Hamaker constant. Its planar pressure magnitude is $\Pi (d)=A/(6\pi d^3)$.

For a nearly planar freezing front, the spherical gap is $d(r)=d_0+r^2/(2a)$. In the particle frame the incoming normal motion has speed $V$. Axisymmetric mass conservation gives the outward gap flux per circumference $q_r=Vr/2$. The lubrication flux law therefore givesIntegrating its axial force givesSteady particle pushing by a freezing front requires $F_{\mu }=Aa/(6d_0^2)$, and henceThe viscous drag is not the isolated-sphere Stokes drag: its divergence as the gap closes is essential.

For the deformed interface let $c=\cos {\theta }_0$ and measure $\theta$ from the sphere's downward pole, as in the original geometry. The height below the remote melting isotherm is $a(\cos \theta -c)$. Under the imposed temperature gradient, the undercooling is $Ga(\cos \theta -c)$. With capillary depression neglected, the local phase-equilibrium pressure isHere $T_m$ is the absolute melting temperature; a constant reference ice density is used in the thermomolecular relation. ThusThe numerical value of $K$ will cancel from the speed relation.

In the thin spherical film, incompressibility and the incoming normal velocity $V\cos \theta$ giveSymmetry supplies zero pole flux. The tangential Couette contribution is smaller by $d/a$ and is negligible at this order. Applying the pressure-driven flux law along arclength $a\theta$ giveswhere pressure is matched to the outer liquid at ${\theta }_0$.

A cap area element is $2\pi a^2\sin \theta d\theta$ and its vertical normal component is $\cos \theta$. Put $y=\cos \theta$. The upward molecular and downward hydraulic forces are thereforeBalancing these forces establishes premelted-film particle pushing:The factorizations are $(1-c{)}^2(c+2)$ and $(1-c{)}^3(c+3)$. They confirm positivity on the physical cap range and provide a numerically better-conditioned shallow-cap expression. Since $h=a(1-c)$, the shallow-cap limit within $d\ll h$ is $V\sim A/(12\pi \mu ah)$; it is not a limit in which the film can be identified with the flat-front gap $d_0$.

The local film formula diverges right at the rim ${\theta }_0$. Accordingly the thin-film calculation is an outer approximation away from a small matching fringe, not a claim of a uniformly thin film at its contact with bulk water. Both integrated stress densities vanish at that rim; in the thin-film limit the fringe contributes only a higher-order correction. Surface-tension curvature, altered thermal gradients or appreciable density-change fluxes would require a different balance.

Four useful interactions are dispersion attraction, electrostatic interaction, capillary attraction and short-range repulsion. Their ranges are relative to atomic contact and depend on geometry and environment.

Van der Waals forces provide an attractive contribution extending beyond direct atomic overlap; for an ideal sphere and plane it scales as $F=-AR/(6z^2)$ in a simple nonretarded model. Electrostatic forces can also be long-ranged: biased conducting surfaces are commonly attractive, whereas charged insulating surfaces can attract or repel depending on their charge and screening.

A capillary meniscus in humid air can pull tip and sample together. It acts over the formation and rupture range of the liquid bridge and can greatly exceed atomically localized forces; it is not a universal interaction in a dry vacuum. At the shortest separations, overlap-related Pauli repulsion provides a steep repulsive contact contribution.

Atomic-scale contact contrast relies on strongly localized short-range tip–surface forces, especially the rapidly varying repulsive interaction in the simple contact-mode picture. Long-range attraction mainly adds a background. Real atomic-resolution imaging also depends on apex structure, stability and operating mode; a generic long-range force alone does not resolve individual surface atoms.

A useful five-part classification is electrostatic double-layer, dispersion, steric, depletion force and solvent-mediated interactions. It is a practical classification rather than a unique exhaustive list.

Electrostatic double-layer forces arise from surface charge and mobile-ion redistribution. Like-charged surfaces often repel; opposite charges can attract. Their range changes with salt screening. London dispersion forces comes from correlated electronic fluctuations and is one contribution to Van der Waals force; its sign and strength across a medium depend on dielectric response.

steric stabilization occurs when adsorbed or grafted layers overlap, increasing chain confinement and/or local osmotic free energy. depletion force arises when smaller nonadsorbing solutes are excluded from a narrow gap: their greater accessible volume outside favors bringing the large particles together. Structured-solvent forces include short-range hydration force and hydrophobic attraction; their microscopic origin differs from the depletion force of an added solute.

The original sketches show double-layer overlap, a polymer-coated gap, depletion force exclusion and solvent structure, alongside a dispersion-potential curve. A realistic suspension can experience several simultaneously. Charge neutrality of a particle does not remove dispersion, steric or solvent-mediated interactions.

In quantitative nanomechanical mapping, the operational adhesion is the magnitude of the most attractive force immediately before detachment on a calibrated retraction curve:Here $k_c$ is the cantilever spring constant and ${\delta }_c$ its deflection after baseline subtraction. The area between approach and retraction relates to dissipated work, whereas the minimum force is a force, not an energy. Chemical attraction, Van der Waals forces and ambient-water capillary bridges can all contribute. Match loading rate and peak load, calibrate deflection sensitivity and $k_c$, compare clean reference surfaces, and control humidity; otherwise different maps may reflect different tips or capillary conditions rather than different specimens.

charge stabilization of colloids supplies repulsion when like-charged surfaces and their electric double layers approach. steric stabilization uses attached or adsorbed molecular layers whose overlap costs conformational and osmotic free energy. Combining both gives electrosteric stabilization; a solvated coating must remain attached and well solvated. A viscous medium slows encounters but does not by itself create an equilibrium repulsive barrier.

DLVO theory adds screened electrostatic repulsion to Van der Waals force. A representative close-gap form isfor equal spheres of radius $a$, with Hamaker constant $A_H$ and inverse Debye–Hückel screening length $\kappa$. The formula is schematic near molecular contact, where hydration, surface roughness and finite ion size matter. A repulsive barrier many $k_{B}T$ high produces kinetic stability even if the primary attractive minimum is deeper than the dispersed state. Entry into that primary minimum generally gives strongly bound aggregation; a shallow secondary minimum can give reversible flocculation.

Adding electrolyte increases $\kappa$, shortens the repulsion and can remove the barrier, enabling fast diffusion-limited aggregation. The critical coagulation concentration is the approximate salt concentration at which this rapid-coagulation regime begins under specified conditions. It is not a universal property of the salt alone. Test the prediction using time-resolved dynamic light scattering or turbidity at controlled particle concentration, pH and temperature; check that added ions do not specifically adsorb or change the surface chemistry.

For two equal spheres, the Derjaguin approximation uses $R_{\mathrm{eff}}=R/2$. A planar nonretarded Van der Waals force interaction has energy per area $W(h)=-A_H/(12\pi h^2)$, soThe force is attractive, with magnitude $13.0\mu \mathrm{N}$, taking separation increase as positive. Using the sphere–plane value of $R_{\mathrm{eff}}$ would overestimate it by a factor of two. The gap is much smaller than either radius, as required. Treat the supplied Hamaker constant as the effective one for the intervening medium; roughness, solvation and molecular-scale contact can modify a literal $1\mathrm{nm}$ experiment.

DLVO theory adds short-range attractive Van der Waals forces to repulsive overlap of the electric double layer. Increasing salt concentration raises the ionic strength and shortens the Debye length, screening the repulsion. The repulsive barrier falls, so thermal collisions can carry particles into the primary attractive minimum and cause colloidal coagulation. An intermediate shallow secondary minimum can instead produce weak, potentially reversible association.

The figure's assignments are a: low salt; b: intermediate salt; c: high salt. Curve a has the largest protective barrier, b a lower barrier and secondary minimum, and c no effective repulsive barrier. This explanation assumes the surface charging chemistry does not independently reverse or radically change the surface potential.

For this self-assembly into a colloidal crystal, four useful elements are building blocks, interactions, environment and reversible dynamics. The building blocks here are nearly monodisperse polymer spheres; their shape and size distribution constrain the accessible packing. Their interactions include excluded volume, Van der Waals forces and electrostatic or steric stabilization, which set the free energy landscape. The aqueous environment supplies temperature, viscosity, ionic strength, confinement and concentration controls. Finally, Brownian motion and rotation must let particles encounter one another and rearrange or detach from incorrect contacts. Attractions that bind every collision irreversibly favour an amorphous aggregate rather than an annealed colloidal crystal. These four categories include both thermodynamic selection and the transport/kinetic access needed to realize it.

$N_1$ and $N_2$ count the microscopic interacting units in bodies 1 and 2. Their positions are ${\mathbf{r}}_i$ and ${\mathbf{r}}_j$; the difference vector gives their pair separation. The positive coefficient $C$ specifies an attractive nonretarded pair energy $-C/r^6$ and has units $\mathrm{J}{\mathrm{m}}^6$.

Hamaker summation approximates a macroscopic interaction from Van der Waals forces by adding these microscopic pair energies. For homogeneous continua, sums are replaced by integrals over the two body volumes with number densities ${\rho }_1$ and ${\rho }_2$. Integrating the geometry changes the distance dependence and produces a Hamaker constant $A_H={\pi }^2{\rho }_1{\rho }_{2}C$ for the stated simple model.

The approximation assumes pairwise additivity, uniform material properties, a known geometry and a separation large enough to use a continuum but small enough for the chosen nonretarded interaction law. It neglects many-body electrodynamic screening, chemical bonding, atomic roughness and short-range repulsion. A medium changes the effective interaction strength; an effective measured $A_H$ across water need not equal a vacuum value inferred from isolated atom pairs.

For smooth uncharged spheres, the basic attraction is the Van der Waals force, arising from correlated electric fluctuations. The Hamaker constant $A_H$ incorporates the particles and intervening medium. For equal spheres of radius $a$ separated by a surface gap $h\ll a$, the near-contact van der Waals attraction of spheres isHere positive force means repulsion, and the attractive case has $A_H>0$. At molecular separation, strong short-range repulsion prevents overlap and replaces the continuum divergence with a deep primary minimum. The energy approaches zero from below at large separation; an uncoated, uncharged attractive pair has no electrostatic barrier.

For illustration, $A_H=10^{-20}\mathrm{J}$, $a=100\mathrm{nm}$ and $h=1\mathrm{nm}$ give $|U|\simeq 8.3\times 10^{-20}\mathrm{J}\simeq 20k_{B}T$ at $300\mathrm{K}$. These are chosen scales, not universal material constants. Such a well can trap particles after a thermal encounter and cause particle aggregation, unless another mechanism such as steric stabilization intervenes. The neutral curve in the figure below shows the attraction regularized by an illustrative contact repulsion.

Creating a liquid surface changes the molecular environment and costs interfacial free energy. In the dispersion-only cleavage model, the attractive Van der Waals force per area has magnitude $A/(6\pi h^3)$. Separating two contacting halves from a molecular cutoff $h_0$ to infinity takes work per areaHere $A_H$ denotes the Hamaker constant, to distinguish it from an area. Cleavage creates two free surfaces, giving the Hamaker estimate of liquid surface tensionThe continuum attraction diverges at zero separation and neglects molecular impenetrability and short-range repulsion. The cutoff is therefore an effective contact separation of molecular size, commonly of order $0.1$–$0.3\mathrm{nm}$, not a limit that can be taken to zero.

An experimental limitation is the strong temperature dependence of surface tension. For water in equilibrium with its vapour, the recommended experimental values decrease from $71.98\mathrm{mN}{\mathrm{m}}^{-1}$ at $25{}^{\circ }\mathrm{C}$ to $58.92\mathrm{mN}{\mathrm{m}}^{-1}$ at $100{}^{\circ }\mathrm{C}$, and the fitted tension vanishes at the critical point. A fixed pairwise cleavage energy misses interfacial entropy, changing density and many-body correlations.^[ref] The dispersion-only model is unsuitable when cohesion is dominated by hydrogen bonds, ionic interactions or metallic bonding; liquid metals are a clear example of the latter failure.

DLVO theory combines the attractive Van der Waals force with repulsion between overlapping electrical double layers. A charged colloid attracts counterions; their electrostatic and osmotic response screens its field over the Debye length. Adding salt generally shortens this range and can lower the repulsive aggregation barrier, allowing particles to reach the strongly bound primary minimum. A shallow secondary minimum can instead give weak reversible association. Whether Brownian encounters cause rapid aggregation depends on barrier heights relative to $k_{B}T$, not just on the sign of the force at one separation.

Adsorbed or grafted polymer layers can provide steric stabilization: overlap costs chain entropy and increases the local osmotic pressure. Nonadsorbing smaller particles or polymers can create a depletion force, because bringing large surfaces together increases the volume accessible to the smaller species. Polymer bridging can be attractive when one chain binds more than one particle. A useful comparison experiment varies salt concentration while monitoring scattered light or aggregation, then repeats with a sterically protected suspension. Charge, solvent quality, polymer coverage and particle size determine which interaction dominates; none is a universal constant of all colloids.