HCl and DCl harmonic stretch comparison

ID: hcl-and-dcl-harmonic-stretch-comparison

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]

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