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For a diatomic molecule, let $V(r)$ be the electronic potential energy at bond length $r$, with the atomic nuclei treated as fixed while finding the electronic energy. Choose zero at infinitely separated chemical atoms in the specified electronic quantum states. If the minimum occurs at $r_e$, the bond potential-well depth isThe bottom of this curve describes an equilibrium bond length, not an attainable motionless vibrational quantum state. Changing the zero of potential energy shifts both endpoints equally and leaves $D_e$ unchanged. A quantum harmonic oscillator approximates the curve near its minimum but rises without limit, so that local approximation alone cannot supply a dissociation asymptote. A Morse potential supplies both a minimum and a finite separated-fragment limit.^[ref]

A covalent bond joins chemical atoms through shared electrons. In the familiar two-centre description, one bond pair contributes to a connection between two atomic nuclei. Sharing means that the electrons belong to the combined arrangement and interact with both atomic nuclei; it does not mean that identifiable dots shuttle along drawn paths. The ^[ref] emphasizes the concentration of electrons between atomic nuclei and the resulting attraction and characteristic separation. The pair picture is especially useful for simple molecules, but is not a universal description of every covalent bond.

A Lewis structure turns this picture into practical bookkeeping. Count the valence electrons, indicate which chemical atoms are connected, and allocate two electrons to each line. A bond pair is shared; a lone pair is assigned to one chemical atom without connecting it to another. A double line represents two bond pairs. Dots and lines record allocations, rather than positions, trajectories, or a measured three-dimensional arrangement. ^[ref]

For molecular hydrogen, ${\mathrm{H}}_2$, each neutral hydrogen chemical atom supplies one valence electron. Thus $1+1=2$ valence electrons make one bond pair, represented by $\mathrm{H}-\mathrm{H}$, with no lone pairs. Each hydrogen counts the same shared pair when checking its two-electron arrangement. The molecule still contains two electrons, not four: counting a pair around both endpoints does not create extra electrons.

For water, ${\mathrm{H}}_2\mathrm{O}$, neutral oxygen supplies six valence electrons and the two hydrogen chemical atoms supply one each: $6+1+1=8$. Two O–H connections consume four electrons as two bond pairs. The remaining $8-4=4$ electrons form two lone pairs on oxygen. Around oxygen, the two bond pairs and two lone pairs count as eight electrons; each hydrogen counts two. The whole water molecule has ten electrons, because two additional oxygen electrons are omitted from this valence electron drawing.

For Ammonia, ${\mathrm{NH}}_3$, the total is $5+3\times 1=8$ valence electrons: five from nitrogen and three from hydrogen. Three N–H connections use six electrons as three bond pairs, leaving two electrons as one lone pair on nitrogen. Thus water and Ammonia have the same total of eight valence electrons but different allocations: two plus two pairs versus three plus one. This small calculation already distinguishes their connectivity without a detailed quantum mechanics calculation.

For molecular oxygen, ${\mathrm{O}}_2$, $6+6=12$ valence electrons give the conventional $\mathrm{O}=\mathrm{O}$ Lewis structure. Its two bond pairs use four electrons, leaving eight as four lone pairs, two on each oxygen. Each oxygen consequently counts eight electrons locally. However, actual molecular oxygen has two unpaired electrons and exhibits paramagnetism: it is attracted into a stronger magnetic field. The all-paired Lewis structure cannot capture this observation. Molecular orbital theory describes the unpaired electrons; the successful counting diagram alone is insufficient. ^[ref]

Why does sharing produce a stable separation? For molecular hydrogen, the electronic arrangement responds as the atomic nuclei approach. Their interactions can lower the energy, but pushing them too close raises it. A curve of potential energy against separation therefore has a local minimum, rather than falling forever. Attraction and repulsion balance there. This is a statement about the combined system, not a claim that stationary electrons sit between otherwise motionless atomic nuclei. ^[ref]

The following Morse potential makes those features calculable. Set $x=r/r_e$, where $r$ is separation and $r_e$ its equilibrium value, and let $D$ be the well depth. With the self-chosen parameter $a=2$, define the dimensionless quantitiesHere $F=-dV/dr$ is the net separating force, obtained from the derivative of the potential energy. Positive $f$ pushes the chemical atoms apart; negative $f$ draws them together. These are illustrative curves with $r_e=D=1$ in chosen units, not measured molecular hydrogen data or fitted parameters.

At $x=1$, $u=-1$ and $f=0$. The second derivative is $u^{\prime \prime }(1)=8>0$, confirming a local minimum. At $x=0.5$, $u=(1-e{)}^2-1\approx 1.9525$; at $x=1.5$, $u=(1-e^{-1}{)}^2-1\approx -0.6004$. As $x$ increases without bound, $u$ approaches zero from below. Thus moving from the well bottom to separated chemical atoms requires an increase of $D$ in this model's potential energy. An actual quantum mechanics dissociation threshold also depends on the initial motion of the atomic nuclei, so the well depth alone is not every measured dissociation energy.

The force panel separates $f$ into a positive term $4e^{-4(x-1)}$ and a negative term $-4e^{-2(x-1)}$. At $x=1$ they are $+4$ and $-4$, cancelling exactly; nearer separations favour the positive term. These are algebraic components of the chosen Morse potential, not separately measured microscopic forces. Their usefulness is to show how a balance arises from the slope of one energy curve.

The beauty of the pair picture is its economy: a few marks summarize connectivity and constrain what a proposed molecule can contain. Its historical anchor is Gilbert N. Lewis's 1916 paper ^[ref], also available as an ^[ref]. Lewis structures remain useful because they answer counting questions quickly; quantum mechanics supplies the richer account when energy, shape, or unpaired electrons matter.

The original solution of the Morse potential model, with finite bound vibrational levels and anharmonic spacings. Physical Review 34, 57–64 (1929).

Author-version scan hosted by the University of Athens: jupiter.chem.uoa.gr/thanost/papers/papers4/PR_34%281929%2957.pdf

Quantizing the stretching coordinate gives a quantum harmonic oscillator with reduced mass $\mu$:Here $v$ is the vibrational quantum number and $\hslash =h/(2\pi )$ the reduced Planck constant. Consecutive energy eigenvalues have gap $\hslash \omega$; the ground state has zero-point energy $\hslash \omega /2$ above the well minimum. The offset $V_0$ cancels from every transition energy.

A short proof uses creation and annihilation operators: with $\ell =\sqrt{\hslash /(\mu \omega )}$, write $q=\ell (a+a^{†})/\sqrt{2}$. The Quantum Hamiltonian becomes $\hat{H}-V_0=\hslash \omega (a^{†}a+1/2)$. Nonnegativity of $a^{†}a$ gives the lowest level; repeated application of $a^{†}$ raises its energy by $\hslash \omega$ each time. This also gives $⟨q{⟩}_v=0$ andThe ground state therefore has a nonzero spread of bond lengths, even though its mean stretching displacement vanishes. A stationary energy eigenstate has a time-independent position probability density; the classical oscillation curve is not a trajectory of an atomic nucleus in that state.

The parabolic model formally extends $q$ to the whole real line, whereas an actual bond length satisfies $r>0$. It is useful for low levels concentrated near $r_e$, with typical stretching displacements much smaller than $r_e$. It fails near breakup of the chemical bond and when neglected anharmonicity becomes substantial.

By Klaus P. Huber and Gerhard H. Herzberg. NIST Chemistry WebBook compilation of diatomic constants.

Cited row: ground $X{}^1{\Sigma }^{+}$ state of hydrogen bromide, ${\omega }_e=2648.975\mathrm{c}{\mathrm{m}}^{-1}$ and ${\omega }_e{x}_e=45.2175\mathrm{c}{\mathrm{m}}^{-1}$. The isotope designation in this table is H81Br. These constants characterize low vibrational levels; an exact global Morse potential is a further modelling assumption.

The quantum Hamiltonian with kinetic energy $p^2/(2\mu )$ and Morse potential has bound energies of the displayed form, where $A=\hslash {\omega }_e$, $B=A^2/(4D_e)>0$ and ${\omega }_e=a\sqrt{2D_e/\mu }$. Adjacent energy differences are $A-2B(n+1)$, distinct and positive over the physical bound-level range. A finite truncation with nonzero adjacent dipole couplings therefore satisfies connected nondegenerate transition chain generates special unitary control. Controllability of such a truncation does not by itself prove controllability on the full space including dissociation states.

Let $u=r-r_e$ measure displacement from the equilibrium bond length and put the minimum of potential energy at zero. The harmonic model and the Morse potential areThe harmonic approximation is a symmetric parabola and has no dissociation limit. The Morse potential has a steep compressed side and a shallower extended side, approaching $D_e$ as $r\to \infty$. Matching the curvatures at the minimum gives $k=2D_e{\alpha }^2$. With $\tilde{\omega }$ denoting a spectroscopic wavenumber rather than an angular frequency, the energy levels areHere $x_e$ is the dimensionless spectroscopic anharmonicity constant. The harmonic spacing is constant, while the Morse oscillator spacing is $E_{v+1}-E_v=hc\tilde{\omega }[1-2x_e(v+1)]$ and decreases as the levels approach dissociation. Only finitely many Morse oscillator levels are bound. The exactly solvable potential was introduced to model this anharmonic behaviour.^[ref]

For the harmonic model put $q=\sqrt{\mu \omega /\hslash }u$, with $\omega =2\pi c\tilde{\omega }$, and $N={\pi }^{-1/4}$. The first three normalized reduced-coordinate wavefunctions areTheir numbers of nodes are zero, one and two, and their parities are even, odd and even. The $v=2$ nodes are at $q=\pm 1/\sqrt{2}$. The diagrams below use analytic curves and arbitrary illustrative scales, with both potentials given the same local curvature.

Put $y=e^{-r/\xi }$. Differentiating the Morse potential givesThe finite-separation minimum has $y=B/(2A)$. ThusThe positive bond-dissociation energy is $D=B^2/(4A)=0.250\mathrm{eV}$, measured relative to the separated-atom value $V(\infty )=0$. This distinguishes the well's negative potential energy from the positive energy required to break the bond.

For the displacement $x=r-a$, the Taylor expansion isConsequentlyThe restoring force is $-\kappa x$ to leading order, identifying the bond's Hooke's law spring constant.

Write the Morse potential relative to its minimum as $V(a+x)=D[e^{-2x/\xi }-2e^{-x/\xi }]$. Expanding one order beyond the harmonic term givesThe negative cubic coefficient means that stretching is softer than compression. Thermal motion therefore has positive mean displacement even though the most probable minimum is at $x=0$.

For thermal expansion of a weakly anharmonic bond, classical equipartition gives $⟨x^2{⟩}_0=k_{B}T/\kappa$. Vanishing mean restoring force, to first anharmonic order, requiresFor a bond free to expand under negligible applied tension, $L=⟨r⟩\simeq a+⟨x⟩$. Its linear thermal expansion coefficient is thereforeKeeping the leading perturbative numerical factor gives $\alpha \simeq 3k_B/(2a\kappa \xi )=5.9\times 10^{-5}{\mathrm{K}}^{-1}$. The question only requires the scale, not that factor. The thermal expansion is positive; a purely harmonic approximation would give zero mean displacement and zero thermal expansion. The local Taylor expansion describes a bound bond and is not a globally stable cubic potential.

Take an invented diatomic molecule with a Morse potential, setting the separated-atom energy to zero:Here $a$ is an inverse length, $r_e$ the equilibrium bond length, and ${\omega }_e=a\sqrt{2D_e/\mu }$, with reduced mass $\mu$. These stipulated parameters describe a simple model, not a measured chemical substance. For the one-dimensional Morse oscillator, energy eigenvalues above the minimum areConsequently,The harmonic estimate $A/2=0.1000\mathrm{eV}$ is slightly larger than this model's exact zero-point energy. The physical bound-level restriction matters: the quadratic expression is not an infinite ladder of vibrational quantum states.

For a separate thermal illustration using this same stipulated $D_0$, assume an ideal gas, fully active molecular rotation of the parent, negligible thermal molecular vibration, and negligible electronic excitation for all species. Each monatomic product contributes $\delta h=5RT/2$; the diatomic molecule contributes $7RT/2$. Thus the net increment is $3RT/2$, with molar gas constant $R$. At $T=300\mathrm{K}$,This last result follows from the stated thermal model, not a universal correction for every chemical bond. Frozen rotations, accessible excited states, different fragment composition, or a condensed phase change the thermal increments.

For a bond free of applied tension, use a local potential energy $V(a+x)=V(a)+\kappa x^2/2+\gamma x^3/6+\cdots$ with $\kappa >0$. Classical equipartition gives $⟨x^2{⟩}_0=k_{B}T/\kappa$; vanishing mean force then yields $⟨x⟩=-\gamma k_{B}T/(2{\kappa }^2)$ to first order in anharmonicity. Thus the linear thermal expansion coefficient is $\alpha =-\gamma k_B/(2a{\kappa }^2)$. For a Morse potential, $\gamma =-3\kappa /\xi$, giving positive expansion $3k_B/(2a\kappa \xi )$. This is a local bound-state approximation; the isolated cubic truncation is not a globally stable equilibrium potential.