The ground-state dissociation energy starts at the lowest vibrational quantum state, with the lowest allowed rotational quantum state and the fragment states explicitly specified. For a diatomic molecule whose fragments are ground-state chemical atoms, omitting any additional rotational correction,where is the vibrational zero-point energy measured upward from the well minimum. The initial molecule already has this energy, so less additional energy is needed to reach the same final limit.[ref]
bond-dissociation energy in theoretical chemistry. definition of bond-dissociation energy in theoretical chemistry: D0 = De minus zero-point vibrational energy
For fragments that are themselves molecules, include their zero-point energies too. Define as the electronic energy difference between separately relaxed products and reactant; then, with consistent rotational conventions,Thus “subtract the parent's zero-point energy” is sufficient for atomic products but generally incomplete for molecular products. An excited final quantum state raises its channel threshold by its excitation energy; that threshold does not become the ground-product just because a detector selects it.
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