A typical example in textbooks about the application of Hellmann–Feynman theorem is calculating ⟨1r2⟩ in hydrogen-like atoms. Wikipedia has a nice demonstration of this. At some point in the Wikipedia derivation is used that
∂n∂ℓ = 1.
But why is eq. (1) true? I know that n=nr+ℓ+1,
but nr is just another variable with different physical meaning, so why is nr independent from ℓ, whereas n is not? The Wikipedia proof for Hellmann–Feynman theorem does not address the problem of independence of different parameters. What variables are kept fixed during the differentiation (1) and why?
The Wikipedia page seems to have only a vague notion of ∂ˆH∂λ and ∂E∂λ, unlike in, e.g., thermodynamics, where all partial derivatives are typically written like (∂U∂V)S,(∂U∂V)p,… so that it is clear which variables are kept fixed during the differentiations.
Answer
The application of Hellmann–Feynman theorem to calculate the expectation value ⟨nℓm|ˆr−2|nℓm⟩ of a radial operator e.g. ˆr−2 does only depend on the radial wave function Rnℓ(r) and not the spherical harmonics Ymℓ(θ,ϕ).
The angular part of the hydrogen-like Hamiltonian ˆH := 12μr2{−ℏ2∂∂rr2∂∂r+ˆL2}−Ze2r,e2 := e204πε0, depends on the angular momentum operator ˆL2. We now replace ˆL2 with its eigenvalue ℏ2ℓ(ℓ+1). The resulting Hamiltonian ˆHℓ := ℏ22μr2{−∂∂rr2∂∂r+ℓ(ℓ+1)}−Ze2r depends on the radial variable r but not the angular variables (θ,ϕ).
Thus we can formally think of space R3 = [0,∞[ × S2 as just a halfline [0,∞[, where the radial variable r lives, as the angular variables (θ,ϕ) have become irrelevant for the problem.
When we eliminate the two-sphere S2, we eliminate spherical symmetry SO(3). Recall that the number ℓ had to be an integer to have finite-dimensional unitary representations of SO(3). But in the radial half-line picture, the number ℓ has lost its geometric meaning, and we can formally proceed with a continuous ℓ∈[0,∞[. This is needed to apply Hellmann–Feynman variational method.
But we still have to solve the radial time-independent Schrödinger equation (TISE) ˆHℓRnℓ(r) = EnRnℓ(r) in this new situation. The upshot is that for real ℓ∈[0,∞[, we still derive a quantization condition, namely, that the bound state energy levels En are still discrete, and that the variable nr := n−ℓ−1 ∈N0 should be a non-negative integer. Here the 'principal number' n∈[0,∞[ is defined to make the standard energy formula for the hydrogen-like bound state energy spectrum En = −Z2α2μc22n2 still hold with the caveat that n might not be an integer! In other words, eq. (7) is a definition of n in terms of the bound state energy En.
Thus if we vary ℓ, we must also vary n by the same amount to keep nr an integer.
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