Solution

ID: past-exam-of-the-chemistry-a-course-of-the-university-of-cambridge/2021/paper-1/a2/c/vi/solution

The trial is even under reflection about the midpoint. The normalized box eigenfunctions satisfy , so orthogonality between even and odd functions gives for even . If the higher odd contributions are neglected, the weighted mean from the quantum variational principle becomes
Rearranging yields the two-level variational contamination estimate
The required assumption concerns the neglected contributions to the energy as well as their small probabilities. Numerically the two-level estimate is . It is not an exact identity: direct expansion of this parabolic trial gives for odd , hence the exact ratio is . The omitted higher odd states account for the difference.

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