Keep the same bond force constant and approximate the nuclear masses of , , and by , , and , respectively. Here is the unified atomic mass unit, and denotes deuterium. These are chosen mass number approximations, not measured atomic masses or natural-abundance averages. With the same chlorine isotope in both molecules,
This is the isotope scaling of diatomic vibration prediction. Doubling the light partner's mass nearly doubles the reduced mass, lowering the frequency by about . The factor differs from because the chlorine partner also moves.
Figure 1.
Isotope substitution slows a stipulated harmonic diatomic bond stretch
. Original approximate mass number model: and unchanged bond force constant. Left: calculated reduced masses and normalized angular frequencies. Right: free classical stretches released from the same small displacement and zero velocity, and , with . This is not a measured time trace or an infrared spectrum. Details.
For the same small initial stretch and zero velocity, both models start with the same internal mechanical energy , but the DCl oscillation period is longer by . In the centre of mass frame, and for HCl; and for DCl. These ratios explain which partner moves and are separate from the change in frequency.
The common- assumption belongs to the leading Born-Oppenheimer approximation: fixed nuclear positions and electric charges determine the electronic potential energy, while nuclear masses govern motion on that curve. Quantitative comparison requires actual atomic masses, departures from that approximation, and separation of anharmonicity and molecular rotation from the measured band. Even with common , the quantum harmonic oscillator predicts a different zero-point energy for each isotope.[ref]
The University of Florida's Rotation Vibration Spectrum of the HCl Molecule, University of Florida laboratory protocol, printed pp. 2–3 and 10–11, uses a scanning Michelson interferometer for Fourier transform spectroscopy. An air-filled silicon-window cell supplies the background. Supervised preparation adds concentrated hydrogen chloride liquid; the cleaned cell subsequently receives DCl liquid. Acquisition settings are identical.
The readout is transmission or absorbance against spectroscopic wavenumber, resolving molecular rotation alongside stretching. Background addresses instrument and cell contributions; cleaning addresses carryover. Excessive absorption impairs analysis. Assigning isotopes and rotational branches precedes fitting band parameters to test isotope scaling of diatomic vibration. These are prescribed measurements, not numerical observations supplied here.[ref]
For a transparent ideal model, add the linear rigid rotor to the harmonic vibrational energy levels and assume the same frequency-valued rotational constant in both vibrational states:
For a spin-free diatomic molecule with no electronic angular momentum, electric-dipole selection rules give for this vibrational absorption. Subtracting initial from final energy eigenvalues yields
These are two rotational branches about the vibrational band origin, not a single stretch line. For stipulated dimensionless values and , the first three R-branch positions are , and the first three P-branch positions are . There is no transition. The numbers illustrate level subtraction; they are not HCl measurements. Real upper and lower rotational constants differ, and centrifugal distortion shifts lines further.