I have an hydrogenic atom, knowing that its ground-state wavefunction has the standard form ψ=Ae−βr with A=β3π, I have to find the best value for β (using the variational method). After having included the Darwin correction HD=Dδ(r) with D=α2πZ2, into the Hamiltonian H0=−12∇2−Zr
I calculated ⟨ψ(β)|−∇22|ψ(β)⟩=⟨ψ(β)|T|ψ(β)⟩=β22 then I thought to use the virial theorem to calculate the part ⟨V⟩: ⟨ψ(β)|−Zr|ψ(β)⟩=⟨ψ(β)|V|ψ(β)⟩=−2⟨ψ(β)|T|ψ(β)⟩=−β2 with the Darwin part left to be easily calculated.
Looking at the solutions that my professor wrote, I've just found a different result:
⟨V⟩=⟨ψ(β)|−Zr|ψ(β)⟩=Zβ⟨ψ(β)|−βr|ψ(β)⟩=−2Zββ22=−βZ
Why's that? Is this somehow related to the fact that I'm going to use the variational method later? Please, help me understand.
Answer
In summary, you can either find a |ψ⟩ that solves the schrodinger equation (and hence the virial theorem) or does not solve the schrodinger equation and then minimize E(β)=⟨ψ(β)|H|ψ(β)⟩.
If you've solved the schrodinger equation then there is nothing to minimize. If you have guessed the right functional form of |ψ(β)⟩ then that function will solve the schrodinger equation only at the minimum value E(β).
What you have is (ignoring the constant A for now) the right functional form of |ψ(β)⟩ which does not satisfy the conditions the virial theorem for all values of β because it does not solve the schrodinger equation for all values of β. We can illustrate this last point.
Calculating H|ψ⟩ for arbitrary β (and ignoring the darwin term),
H|ψ⟩=(βr−β22−Zr)|ψ⟩
(up to a multiplicative constant.) Since E must be independent of r we find that β must equal Z. This is what you've found by demanding that the virial theorem holds. This leaves you with the familiar result that
E=−Z22.
Notice that if you try to apply the virial theorem and then the variational method, the total energy E(β)∼−β2, which as you can see is unbounded from below. You can't minimize this! Your professor's approach is correct -- show yourself that you can minimize ⟨T⟩+⟨V⟩ to conclude that β=Z.
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