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In perturbation theory, wave function of a perturbed system can be expressed in a power series of some $\lambda$ as $\psi^{(0)} + \lambda\psi^{(1)}+\lambda^2\psi^{(2)}......$.

Then we express Hamiltonian operator as $H^{(0)} + \lambda H^{(1)}$.

Introduction of $\lambda$ in $\psi$ can be understood but why we introduce $\lambda$ in Hamiltonian operator and what is the significance of this $\lambda$ factor.

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  • $\begingroup$ You use it but it does not appear in the final result. It is used to sort out zero, first, second etc powers of perturbation. In chemical terms very loosely sort of like a catalyst. $\endgroup$
    – porphyrin
    Commented May 1, 2020 at 7:20
  • $\begingroup$ For distinguishment purpose, we can introduce $\lambda$ in $\psi$ but why in Hamiltonian operator. Why we can't write $H$ as just $H^{(0)}+H^{(1)}$. As it also gives first order correction as $\lambda$ is present in $\psi$ while solving Schrödinger's equation? $\endgroup$
    – Manu
    Commented May 1, 2020 at 7:25
  • $\begingroup$ If you write $H$ as just $H^{(0)}+H^{(1)}$, then you don't know which of these is big, and which is small, and which is to be neglected. $\endgroup$ Commented May 1, 2020 at 7:31
  • $\begingroup$ Also when I solve Schrödinger's equation using $H$ as $H^{(0)}+H^{(1)}$, I get ($H^{(0)}+H^{(1)}$)× $\psi$ = $E^{(0)}$*$\psi$, which is a contradiction as it implies $H^{(1)}=0 but system is perturbed. $\endgroup$
    – Manu
    Commented May 1, 2020 at 7:41
  • $\begingroup$ I don't understand your argument, i.e, to compare $H^{(1)}$ and $H^{(0)}$. Please explain a bit more. $\endgroup$
    – Manu
    Commented May 1, 2020 at 7:45

1 Answer 1

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The method is only outlined below, the full details should be in your textbook or lecture notes.

Your $H^{(1)}$ is just the (small) perturbing potential energy added to the original hamiltonian so you could write $H^{(0)}+\lambda V$. ($\lambda$ is dimensionless and varies from 0, no perturbation, to 1, full perturbation ).

The Schroedinger equation is now $(H^{(0)}+\lambda V)\varphi_n=E_n\varphi_n$ where $\varphi_n,\; E_n$ are the new wavefunctions and energy. These are expanded as a Taylor series in $\lambda$, e.g. $\displaystyle \varphi_n \approx \varphi_n^0 + \lambda \frac{d\varphi_n}{d\lambda}+\frac{\lambda^2}{2!} \frac{d\varphi_n^2}{d\lambda^2}+ ..\equiv \varphi_n^{(0)}+\lambda\varphi^{(1)}_n +\lambda^2\varphi^{(2)}_n+..$ and similarly for $E_n$.

Next this result and that for $E_n$ are substituted back into the Schroedinger eqn and powers of $\lambda$ factored out. These remaining equations are solved but none now contain $\lambda$; for example the first order term is $\lambda\left((V-E^{(1)}_n)\varphi^{(0)}_n+(H^{(0)}-E_n^{(0)})\varphi^{(1)}\right)$ where in this new notation $\varphi^{(0)}$ is the original unperturbed wavefunction and similarly for the energy.

The equation to solve is now $(V-E^{(1)}_n)\varphi^{(0)}_n+(H^{(0)}-E_n^{(0)})\varphi^{(1)}=0$.

After (formally) integrating the equation some fiddling around you find that $\varphi^{(1)}$ is needed. The important step now is to expand this wavefunction in terms of the original basis set of unperturbed wavefunctions $\phi$. This can be done because these form a complete orthonormal set, thus $\varphi^{(1)}= \sum_k a_k\phi_k$ where $a_k$ are the expansion coefficients and these have to be found. Again after some more fiddling with equations and using the orthonormality of the $\phi_n$ the perturbation energy $E^{(1)}_n = \int \varphi^{(0)*}_nV\varphi^{(0)}_nd\tau = \int\phi^{0*}V\phi^0 d\tau$.

Notice how only the unperturbed wavefunctions contribute to the energy. The new wavefunction is $$ \varphi^{(1)}_n=\sum_{n\ne k} \frac{E_n^{(1)}}{E_n^{(0)}-E_k^{(0)}}\varphi^{(0)}$$

which is a linear combination of the unperturbed wavefunctions with the $a$ coefficients as ratio of energies.

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  • $\begingroup$ As we use $d\psi_n/d\lambda$, it can happen that the wave function may not be continuous with respect to $\lambda$ or is not differentiable at a particular $\lambda$, because the postulates of quantum mechanics specify that wave function is continuous with respect to x,y and z, not with respect to some other quantity like extent of perturbation($\lambda$). Do we assume that $\psi$ is also continuous for $\lambda$? $\endgroup$
    – Manu
    Commented May 1, 2020 at 9:24
  • $\begingroup$ It has to be assumed that the derivatives behave normally, but as it happens its only a formal differentiation, and then integration; the wavefunction is only used symbolically. Only the unperturbed wavefunctions are used to calculate first order and the function for these (say sin, cos , exp etc. ) are known by solving the unperturbed equation, and as the $V$ is known and also the $E_n$ the wavefunction for $\varphi^{(1)}$ can be calculated. $\endgroup$
    – porphyrin
    Commented May 1, 2020 at 10:20

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