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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]

Let $r$ be the instantaneous bond length, $r_e>0$ its equilibrium value, and $q=r-r_e$ the stretching displacement. Assume one fixed electronic quantum state, a smooth potential energy $V(r)$ with a nondegenerate local minimum at $r_e$, and omit molecular rotation initially. The Taylor series has no linear term because $V^{\prime }(r_e)=0$:Keeping only the quadratic term is the harmonic approximation near a potential minimum. The bond force constant $k$ has units $\mathrm{N}{\mathrm{m}}^{-1}$. It measures local stiffness; it is not the bond-dissociation energy, which concerns the depth and distant shape of the entire well.

The two-particle relative coordinate explains the reduced mass. For stretching along a fixed axis in a stationary centre of mass frame, let $u_1,u_2$ be the nuclear displacements from equilibrium. Then $u_2-u_1=q$ and $m_1{u}_1+m_2{u}_2=0$, soHere $T$ is the internal kinetic energy, and $m_1,m_2>0$ are the two nuclear masses. The lighter partner moves farther; the reduced mass is smaller than either individual mass. The restoring force $-dV/dq\simeq -kq$ gives simple harmonic motion:The angular frequency is $\omega$, the ordinary frequency is $\nu$, and ${\tilde{\nu }}_{\mathrm{harm}}$ is the corresponding spectroscopic wavenumber; $c$ is the speed of light. Use $c$ in $\mathrm{cm}{\mathrm{s}}^{-1}$ to obtain ${\tilde{\nu }}_{\mathrm{harm}}$ in $\mathrm{c}{\mathrm{m}}^{-1}$. The symbol $k$ here is a bond force constant, not an angular wavenumber.

For an original dimensionless example, choose $m_1=m_2=2$ and $k=4$ in consistent model units. Then $\mu =1$ and $\omega =2$. Releasing at $q(0)=0.1$ with $\dot{q}(0)=0$ gives $q(t)=0.1\cos (2t)$ and $u_1=-q/2$, $u_2=q/2$. Each atomic nucleus moves only half the stretching amplitude, while the conserved internal mechanical energy above $V_0$ is $\frac{1}{2}k(0.1{)}^2=0.02$. Fixing one partner instead would give $\omega =\sqrt{2}$, demonstrating why a one-body calculation changes the model.

Cited row: $3d^{7}4s^{2}a{}^4{F}_{9/2}$ at zero spectroscopic wavenumber. This is a measured atomic-level compilation, not an answer set for any examination.

Cited row: $3d^{10}({}^{1}S)4s{}^2{S}_{1/2}$ at zero spectroscopic wavenumber. The table distinguishes the neutral atom from the closed-shell copper(I) ion.

An actual infrared spectroscopy route is to compare gaseous hydrogen chloride containing ordinary hydrogen with its deuterium counterpart. A documented teaching experiment uses a stopcock-equipped gas cell with potassium bromide windows and a Nicolet Avatar instrument for Fourier transform spectroscopy. A nitrogen-purged flask and drying tube supply the mixture; the sample also contains sulfur dioxide. An empty sample-chamber background precedes the filled-cell scan. The absorbance trace and peak-picked spectroscopic wavenumbers are the readout. The analysis assigns and indexes ${}^1{\mathrm{H}}^{35}\mathrm{Cl}$ and ${}^2{\mathrm{H}}^{35}\mathrm{Cl}$ transitions separately and propagates transition uncertainties. The instructions distinguish resolvable chlorine isotope peaks from adequate precision for the intended parameter analysis. ^[ref]

A separate published teaching dataset reports a Nicolet Nexus 670 instrument, a $10\mathrm{cm}$ gas cell at $20\mathrm{Torr}$, and chlorine isotope peaks resolved to baseline. These apparatus details describe that dataset, not the preceding experiment. ^[ref]

The inference connects several models. Fit correctly assigned transitions to separate molecular rotation from molecular vibration, then compare the inferred vibrational scales using isotope scaling of diatomic vibration. Agreement supports the approximate separation between a nearly unchanged chemical bond stiffness and a changed nuclear mass. It does not make a real molecule an exact classical spring: anharmonicity shifts the fundamental transition away from the local harmonic oscillator scale, and coupling to molecular rotation shifts individual lines.

For an independent test, calculate the reduced masses from the specified isotopes and compare the inferred values $k=\mu (2\pi c{\tilde{\nu }}_{\mathrm{harm}}{)}^2$. Agreement within uncertainty tests the common-curvature assumption; choosing separate $k$ values just to fit each frequency would not test it. The documented background addresses instrument and ambient contributions, but does not by itself subtract window absorption, identify contaminating species, or calibrate the spectroscopic wavenumber scale. Those require separate controls. Finite spectral resolution, blended peaks, incorrect isotope assignments, and departure from the harmonic approximation near a potential minimum limit the comparison. No numerical measured line positions are assumed here.

The diatomic molecule containing one hydrogen atom and one iodine atom. Its measured spectroscopic wavenumbers include anharmonic corrections beyond the two-term Morse oscillator model.^[ref]

For emission take integers $n_i>n_f\ge 1$. Applying conservation of energy to the model's internal energy difference, while neglecting the much smaller whole-atom photon recoil, givesThus Johannes Robert Rydberg's Rydberg formula is a difference of two energy levels expressed as a spectroscopic wavenumber. The same constants determine every line; there is no new parameter for each electronic transition. With the chosen inputs, $R_H=1.096775834\times 10^7{\mathrm{m}}^{-1}$. All wavelengths below are calculated in vacuum, not air, and are rounded model predictions rather than historical measurements.

The conventional names commemorate Theodore Lyman and Johann Jakob Balmer. Fixing $n_f=1$ produces the ultraviolet Lyman series, beginning with the Lyman-alpha line; fixing $n_f=2$ produces the Balmer series. As $n_i\to \infty$, the wavelength approaches $n_f^2/R_H$: $91.1763\mathrm{nm}$ at the Lyman limit and $364.705\mathrm{nm}$ for the Balmer series. Crowding follows directly from $E_{n+1}-E_n\sim 2B_H/n^3$. Discreteness therefore coexists with a series limit.

Correct line positions do not give wave intensities, lifetimes or electric-dipole selection rules for hydrogen. Those require a theory of the wavefunctions and their coupling to electromagnetic radiation. The circular model also omits spin, relativistic corrections and the Lamb shift. Its successful gross energy levels do not make its assumed orbits modern atomic orbitals.

Near a stable equilibrium bond length $r_e$, a Taylor expansion of a diatomic molecule's potential energy gives $U(r)\simeq U(r_e)+k(r-r_e{)}^2/2$, with $k=U^{\prime \prime }(r_e)>0$. Treat the internal stretch as a harmonic oscillator of reduced mass, initially omitting molecular rotation. If replacing an isotope leaves this local potential energy curvature unchanged, thenHere $c$ is the speed of light and ${\tilde{\nu }}_{\mathrm{harm}}$ a spectroscopic wavenumber; use consistent length units for $c$ and ${\tilde{\nu }}_{\mathrm{harm}}$. The quantum harmonic oscillator gives adjacent energy eigenvalues separated by $h\nu$, with $h$ the Planck constant. Consequently a vibrational photon absorption can probe the same frequency scale, subject to electric-dipole selection rules.

For an explicitly approximate isotope example, assign the atomic masses of ${}^1\mathrm{H}$, ${}^2\mathrm{H}$, ${}^{35}\mathrm{Cl}$, and ${}^{37}\mathrm{Cl}$ the mass-number values $1u,2u,35u,37u$, respectively, with $u$ the unified atomic mass unit. These are stipulated approximations to individual atomic masses, not measured masses of molecules or natural-abundance averages. They giveThe symbol $\mathrm{D}$ means deuterium, ${}^2\mathrm{H}$. Doubling the light partner's approximate atomic mass therefore produces a large predicted shift, whereas changing the already heavy chlorine partner by two mass units produces a much smaller one. A quantitative comparison with infrared spectroscopy requires actual isotope-specific atomic masses, fitted band parameters, and uncertainties, rather than identifying any arbitrary peak with ${\tilde{\nu }}_{\mathrm{harm}}$.

A useful vibration-rotation expression, with energies measured from the potential minimum, isHere $v=0,1,\dots$ is the vibrational quantum number, $J=0,1,\dots$ the rotational angular-momentum quantum number, ${\tilde{\nu }}_e$ the harmonic spectroscopic wavenumber, $x_e$ a dimensionless anharmonic coefficient, and $B_v$ the vibrational-state-dependent rotational constant. $B_e$ is its equilibrium value and ${\alpha }_e$ describes vibration-rotation coupling. All wavenumber constants use the same inverse-length units; $h$ is the Planck constant and $c$ the speed of light.

The elementary harmonic rigid rotor result follows by setting $x_e={\alpha }_e=0$, with ${\tilde{\nu }}_e=(2\pi c{)}^{-1}\sqrt{k/\mu }$ and $B_e=h/(8{\pi }^{2}cI)$, where $I=\mu r_e^2$. The molecule's electronic energy would add a common constant.

Use the two-body reduced mass, rather than the chlorine mass or hydrogen mass alone:The bond force constant givesThe requested “frequency in cm−1” is a spectroscopic wavenumber; the ordinary frequency is the value in s−1 above. This calculation uses the question's force constant in the harmonic model, rather than replacing it with a tabulated spectroscopic constant.

The carbon end of a carbonyl ligand has a filled $5\sigma$ molecular orbital with an outward-facing lobe. Its overlap with a vacant metal orbital of the same axial symmetry gives CO-to-metal sigma donation. Occupied metal $d_{\pi }$ orbitals can simultaneously overlap with the empty CO $2{\pi }^{\ast }$ antibonding molecular orbitals, giving metal-to-CO pi backbonding. Two perpendicular pi channels are possible; the schematic represents one. Orbital signs indicate phase, not electric charge.

The two interactions reinforce one another: sigma donation transfers density toward the metal, and pi backbonding distributes it into the ligand acceptor orbitals. Both strengthen M–C attachment, while backbonding weakens C–O. Occupation of CO ${\pi }^{\ast }$ decreases the internal C–O bond order, generally increasing its bond length and lowering its stretching spectroscopic wavenumber. This is why a strongly backbonded carbonyl ligand can have a strong metal–carbon bond and a weakened internal carbon–oxygen bond at the same time.

The relevant spectrochemical series order is O-bound nitrito $<$ Ammonia $<$ N-bound nitro. A pi-donor ligand tends to raise the metal orbitals derived from $t_{2g}$, reducing the octahedral splitting; a pi-acceptor ligand stabilizes those orbitals, increasing the splitting. Since photon energy is $E=hc/\lambda$, the stronger-field complex absorbs at the shorter wavelength. ThusThe corresponding spectroscopic wavenumbers are approximately $21834$, $21097$ and $20576\mathrm{c}{\mathrm{m}}^{-1}$. These are the observed band energies, not three exact independent determinations of ${\Delta }_o$: low-spin $d^6$ transition energies also contain electron repulsion contributions, and replacing one ligand lowers the ideal octahedral symmetry. The relative assignment is nevertheless robust.

A carbonyl ligand binds through carbon, whose occupied $5\sigma$ molecular orbital has a substantial outward-facing carbon lobe. Overlap with an empty metal orbital along the M–C axis gives ligand-to-metal sigma donation. Conversely, an occupied metal $d_{\pi }$ orbital overlaps sideways with an empty CO $2{\pi }^{\ast }$ antibonding molecular orbital, giving metal-to-ligand pi backbonding. There are two mutually perpendicular pi channels. The original orbital schematic below shows one of them; $+$ and $-$ denote orbital phase, not electric charge.

The interactions are synergic: donation makes electron density available at the metal, and backbonding helps accommodate it while strengthening the metal–carbon interaction. Occupying CO ${\pi }^{\ast }$ reduces the C–O bond order, lengthens that bond and lowers its bond force constant. Therefore stronger pi backbonding generally lowers the carbonyl stretching spectroscopic wavenumber even while strengthening the M–C attachment.

The diagnostic infrared spectroscopy absorptions are the conjugated ester carbonyl near $1720\mathrm{c}{\mathrm{m}}^{-1}$ and the alkene stretch near $1650\mathrm{c}{\mathrm{m}}^{-1}$. Reasonable approximate ranges are $1715$–$1730$ and $1620$–$1660\mathrm{c}{\mathrm{m}}^{-1}$, respectively. Conjugated system lowers the carbonyl stretching spectroscopic wavenumber relative to an unconjugated ester.

The ester C–O stretches and strong C–F stretches lie mainly in the $1000$–$1300\mathrm{c}{\mathrm{m}}^{-1}$ region. Vinylic C–H stretching is just above $3000\mathrm{c}{\mathrm{m}}^{-1}$, and saturated C–H stretching is about $2850$–$3000\mathrm{c}{\mathrm{m}}^{-1}$. There is no hydroxy group to give a broad O–H band.

Taking the Hessian of the potential with respect to mass-weighted displacements givesThe equations of motion are $\ddot{\mathbf{q}}=-D_0\mathbf{q}$, so eigenvalues are squared angular frequencies. Normalized eigenvectors and frequencies areBoth vectors are in the q basis, and $\mu =m_a{m}_b/(m_a+m_b)$. The translation corresponds to equal physical displacements $\delta y_a=\delta y_b$. The stretch has $m_a\delta y_a+m_b\delta y_b=0$ and opposite physical displacements with magnitude ratio $|\delta y_a/\delta y_b|=m_b/m_a$. Ordinary frequencies are $\nu =\omega /(2\pi )$; spectroscopic wavenumbers are $\omega /(2\pi c)$.

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.

Express the rotational constant as a spectroscopic wavenumber $\tilde{B}=h/(8{\pi }^{2}cI)$. The rotational absorption selection rule $\Delta J=+1$ givesSuccessive lines therefore have spacing $2\tilde{B}$, regardless of the starting $J$. Both observed spacings are $20.88\mathrm{c}{\mathrm{m}}^{-1}$, giving $\tilde{B}=10.44\mathrm{c}{\mathrm{m}}^{-1}$. The three lines are consequently the $5\to 6$, $6\to 7$ and $7\to 8$ transitions within the stated precision; the first observed line is not the $0\to 1$ line.

Using the given isotopic masses, the reduced mass isWith $\tilde{B}=1044{\mathrm{m}}^{-1}$ and $c$ in $\mathrm{m}{\mathrm{s}}^{-1}$, the bond length follows fromThe small common $0.01\mathrm{c}{\mathrm{m}}^{-1}$ offset relative to integer multiples of the spacing is immaterial at the precision of this model. A real ground-vibrational-state rotational constant determines an effective vibrationally averaged bond length; it need not equal the exact equilibrium separation.

Pi backbonding is donation from occupied metal orbitals into ligand acceptor orbitals with pi symmetry about the metal–ligand axis. In a carbonyl ligand, occupation of CO ${\pi }^{\ast }$ weakens C–O while strengthening metal–carbon bonding. Lower CO stretching spectroscopic wavenumber is therefore a useful comparative probe, with electrostatic and mode-coupling qualifications.

The signed Raman shift subtracts scattered from incident spectroscopic wavenumber:Here $c$ is the speed of light, and both wavelengths are in vacuum. Positive shifts denote Stokes Raman scattering; negative shifts denote Anti-Stokes Raman scattering. Some plots reverse the horizontal direction or report separate unsigned magnitudes, so check the convention. Spectroscopic wavenumber has no $2\pi$ factor, unlike the common angular wavenumber $k=2\pi /\lambda$. A shift of $1000\mathrm{c}{\mathrm{m}}^{-1}$ means $100000{\mathrm{m}}^{-1}$, not a frequency of $1000\mathrm{Hz}$.

For a one-quantum change of molecular vibration with ordinary frequency ${\nu }_v$, the magnitude is ${\tilde{\nu }}_v={\nu }_v/c$. This makes Raman spectroscopy attractive: the same molecular energy spacing can be read using different visible excitation wavelengths. Equal and opposite Raman shifts are not equal and opposite changes measured in nanometres, because wavelength is the reciprocal of spectroscopic wavenumber.

In this article the rotational constant is a frequency,Its dimensions are ${\mathrm{s}}^{-1}$, since the Planck constant has dimensions $\mathrm{kg}{\mathrm{m}}^2{\mathrm{s}}^{-1}$ and a moment of inertia has dimensions $\mathrm{kg}{\mathrm{m}}^2$. Some authors instead call $hB={\hslash }^2/(2I)$ the energy-valued rotational constant; this is the convention in the earlier synthetic molecular beam electric resonance diagram. A third convention uses the spectroscopic wavenumber $\tilde{B}=B/c$, with $c$ the speed of light. Always check units before using $\nu =2B(J+1)$.

If $B$ is known and the two masses are specified, the rigid two-atom model gives the bond length $r=\sqrt{h/(8{\pi }^2\mu B)}$. This is why rotational spectroscopy can constrain molecular geometry. A real fitted constant can depend on molecular vibration, so this inference alone does not establish an equilibrium bond length.