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A bond-dissociation enthalpy is the molar enthalpy change for the specified homolysis at temperature $T$, with reactant and products in specified standard states. Its usual units are $\mathrm{kJ}\mathrm{mo}{\mathrm{l}}^{-1}$. The superscript $\circ$ specifies standard states; it does not fix $T$ to room temperature.^[ref]

Write $\delta h_i(T)=H_{m,i}^{\circ }(T)-H_{m,i}^{\circ }(0)$ for each species' molar thermal enthalpy increment. With $D_0$ an energy per parent molecule,Here $N_{\mathrm{A}}$ is the Avogadro constant. The thermal increments include translational kinetic energy, molecular rotation, thermally excited molecular vibration and electronic states when populated, and the $pV$ contribution to enthalpy. They are additional to the zero-point energies already included in $D_0$. If values of standard enthalpy of formation at the same $T$ are available, Hess's law gives the same quantity as ${\Delta }_f{H}^{\circ }(A)+{\Delta }_f{H}^{\circ }(B)-{\Delta }_f{H}^{\circ }(AB)$.

Units alone do not identify the convention. Multiplying either $D_e$ or $D_0$ by the Avogadro constant gives molar energy, but does not add thermal enthalpy. One electronvolt per dissociation corresponds to $96.485332\mathrm{kJ}\mathrm{mo}{\mathrm{l}}^{-1}$. A spectroscopic wavenumber $\tilde{\nu }$ represents energy $hc\tilde{\nu }$, using the Planck constant $h$ and speed of light $c$; $1\mathrm{c}{\mathrm{m}}^{-1}$ corresponds to $0.011962657\mathrm{kJ}\mathrm{mo}{\mathrm{l}}^{-1}$.^[ref]

Molecular rotation changes a molecule's orientation. Its rotational kinetic energy depends on the arrangement and masses of its chemical atoms. A rigid rotor freezes internal distances to isolate this motion; rotational spectroscopy tests the resulting energy eigenvalues through transitions between quantum states. The molecular beam electric resonance experiment provides a complementary probe of the coupling to an electric field.

Molecular vibration changes internal separations and bond angles, unlike the fixed internal molecular geometry of a rigid rotor. Its coupling to molecular rotation makes measured rotational constants depend on the vibrational quantum state.

Rotational spectroscopy probes transitions between molecular rotation quantum states. In the simple linear rigid rotor, line spacing determines a moment of inertia, while an isotope shift of a linear rotor tests the mass dependence. More general molecular geometry requires several principal moments of inertia and more complicated assignments. The combination makes spectra sensitive fingerprints of both composition and shape.

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.