Isotope scaling of diatomic vibration (${\nu }^{\prime }/\nu \simeq \sqrt{\mu /{\mu }^{\prime }}$)

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 ${\tilde{\nu }}_{\mathrm{harm}}$.