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I am considering an unperturbed Hamiltonian of the form:

$$H_0 \equiv -\dfrac{\hbar^2}{2m} \dfrac{d^2}{dx^2} - \alpha\, \delta(x),$$

which has a single bound state solution given by $$\psi^{(0)}(x) = \sqrt{\dfrac{m\alpha}{\hbar}} \exp\left(-\dfrac{m\alpha}{\hbar^2} |x|\right),$$ with energy eigenvalue $$E^{(0)} = -\dfrac{m\alpha^2}{2\hbar^2}.$$

Now, I introduce a sinusoidal perturbation to this system: $$H' = a\,\sin(kx).$$

The first-order energy correction is straightforward to compute: $$E^{(1)} = \int_{-\infty}^{+\infty} \psi^{(0)*}(x) \, H'(x) \, \psi^{(0)}(x) \, dx = -\frac{ma\alpha}{\hbar^2} \int_{-\infty}^{+\infty} \exp\left(-\dfrac{2m\alpha}{\hbar^2} |x|\right) \sin(kx) \, dx = 0.$$

However, when I try to compute the second-order energy correction, $$E^{(2)}_n = \sum_{k \neq n} \dfrac{\left|\langle k^{(0)} | H' | n^{(0)} \rangle \right|^2}{E_n^{(0)} - E_k^{(0)}},$$ I encounter a problem. In this system, there is only one energy eigenvalue and eigenstate for the bound state. Thus, it seems that the second-order correction, and similarly the third-order and higher-order corrections, cannot be computed.

So my questions are:

  1. Is it true that there are no second-order or higher-order corrections to the eigenstate and energy in this case?

  2. If so, since the first-order energy correction $E^{(1)}$ vanishes, does this mean the spectrum of $H_0$ and $H_0 + H'$ remains completely identical? How can this be interpreted physically?

2 Answers2

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  1. It is not true. The expression that you are using for higher corrections of the energy levels include the corrections in the eigenstate $\psi^{(0)}$, which in turn is obtained using a resolution of identity . In other words, the expression that you are using only makes sense if you know all unperturbed eigenstates of the unperturbed Hamiltonian, such a way that they form a complete basis, i.e., $\int dk \left|k^{(0)}\right \rangle\!\left \langle k^{(0)}\right| = \mathbb I$. You could read more in the wiki.

The thing is that there is only one bound eigenstate, so it is not a complete basis, then you should include the unbounded eigenstates to complete the basis. It makes sense, since you should take into account that the perturbation could induce a transition of bounded to unbounded state, setting free the particle.

I would recommend you to calculate the correction $\psi^{(1)}$ first, before going into $E^{(2)}$.

I would also recommend the reference [1] for a review about Delta Potentials and the completeness relation, and its use in perturbation theory (with different potential, but you could take notes).


[1] The infinite well and Dirac delta function potentials as pedagogical, mathematical and physical models in quantum mechanics chapter 6.3

Ruffolo
  • 4,397
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In "simple" one-dimensional cases like this, one can often solve the first-order Schrödinger equation analytically: $$ \Big[H^{(0)}-E^{(0)}\Big]|\psi^{(1)}\rangle=-\Big[W-E^{(1)}\Big]|\psi^{(0)}\rangle $$ as an inhomogeneous differential equation to find the exact first-order wave function. Then the second- and third-order energies can be readily computed, and the pain of dealing with scattering states is avoided, because not a single sum-over-states appears in our perturbation formulae.

To keep things simple, I start with natural units $\hbar=c=1$, so that $$ H=-\frac{1}{2m}\frac{\mathrm{d}^2}{\mathrm{d} x^2}-\alpha\delta(x)+a\sin(kx) \ , $$ where $\delta(x)$ has dimension $1/\text{length}=\text{energy}$, so $\alpha$ is dimensionless. Let us introduce the energy and length scales $$ {\cal{E}}_0=m\alpha^2 \ \ \ , \ \ \ l_0=\frac{1}{m\alpha} \ . $$ Then the dimensionless problem reads $$ {\cal{H}}=\frac{1}{{\cal{E}}_0}H=-\frac{1}{2}\frac{\mathrm{d}^2}{\mathrm{d} {x'}^2}-\delta(x')+q\sin(\kappa x') \ , $$ where $q=a/{\cal{E}}_0$, $\kappa=kl_0$ and $x'=x/l_0$ (but I will name it as $x$ from now on for simplicity). The zeroth-order solution is just $$ \psi^{(0)}(x)=\exp(-|x|) \ \ , \ \ E^{{(0)}}=-\frac{1}{2} \ , $$ and $E^{{(1)}}=0$. The first-order Schrödinger equation reads $$ \left[-\frac{1}{2}\frac{\mathrm{d}^2}{\mathrm{d} x^2}-\delta(x)+\frac{1}{2}\right]\psi^{(1)}(x)=-q\sin(\kappa x)\exp(-|x|) \ . $$ Since $\psi^{(0)}(x)$ is even and the perturbation is odd, we expect from symmetry considerations that $\psi^{(1)}(x)$ is odd. This means $\psi^{(1)}(0)=0$, so the delta function term can be dropped: $$ \left[-\frac{1}{2}\frac{\mathrm{d}^2}{\mathrm{d} x^2}+\frac{1}{2}\right]\psi^{(1)}(x)=-q\sin(\kappa x)\exp(-|x|) \ . $$ The well-behaving solution for $x>0$ is $$ \psi^{(1)}_+(x)=c_+\exp(-x)+\frac{2q}{\kappa(4+\kappa^2)}\Big[2\cos(\kappa x)-\kappa\sin(\kappa x)\Big]\exp(-x) \ , $$ and for $x<0$, it is $$ \psi^{(1)}_-(x)=c_-\exp(+x)-\frac{2q}{\kappa(4+\kappa^2)}\Big[2\cos(\kappa x)+\kappa\sin(\kappa x)\Big]\exp(+x) \ . $$ Matching the two solutions as $x\rightarrow0$ leads to the relation $$ c_+-c_-=-\frac{8q}{\kappa(4+\kappa^2)} \ . $$ We need one more condition to completely fix the first-order wave function, the intermediate normalization: $$ \langle\psi^{(0)}|\psi^{(1)}\rangle=\int_{-\infty}^0\mathrm{d}x\psi^{(0)}(x)\psi^{(1)}_-(x)+\int_0^{+\infty}\mathrm{d}x\psi^{(0)}(x)\psi^{(1)}_+(x)=0 \ . $$ After carrying out the integrals, we find $c_++c_-=0$ from this condition, so $$ c_\pm=\mp\frac{4q}{\kappa(4+\kappa^2)} \ , $$ and $\psi^{(1)}(x)$ is completely determined: $$ \psi^{(1)}(x)=-\frac{2q}{4+\kappa^2}\text{sgn}(x)\left[2\frac{1-\cos(\kappa x)}{\kappa}+\sin(\kappa |x|)\right]\exp(-|x|) \ . $$ The solution has odd parity and vanishes at $x=0$, as expected.

The second-order energy is then $$ E^{(2)}=\langle\psi^{(0)}|W|\psi^{(1)}\rangle=-\frac{\kappa^2(10+\kappa^2)}{(1+\kappa^2)(4+\kappa^2)^2}q^2 \ , $$ manifestly negative, as all second-order corrections to ground state energies should be. Because of the $2n+1$ theorem of Wigner, knowing $\psi^{(1)}(x)$ would be sufficient to determine the third-order energy as well: $$ E^{(3)}=\langle\psi^{(1)}|W|\psi^{(1)}\rangle-E^{(1)}\langle\psi^{(1)}|\psi^{(1)}\rangle \ , $$ but this is of course zero due to parity reasons, just like $E^{(1)}$ was.

So in conclusion, the energy of the perturbed system seems to be $$ E=-\frac{1}{2}-\frac{\kappa^2(10+\kappa^2)}{(1+\kappa^2)(4+\kappa^2)^2}q^2+{\cal{O}}(q^4) \ . $$

This system is very special because the unperturbed Hamiltonian has only a single bound state, so all perturbation contributions come from the continuum part of the zeroth-order spectrum. But actually, continuum states are always important in perturbation theory, even if one has an infinite number of zeroth-order bound states (like in the case of the hydrogen atom). I prepared some examples of this (probably surprising) phenomenon in an earlier answer.