Solution

ID: past-exam-of-the-chemistry-a-course-of-the-university-of-cambridge/2022/paper-2/a9/b/i/solution

The opposite spatial parity of the s orbital and axial p orbital gives opposite signs for left and right – hopping. With real , one consistent Bloch-basis convention gives
The resulting energies are
Thus s-p mixing in a one-dimensional tight-binding chain lowers the lower branch and raises the upper branch wherever the coupling is nonzero. For separated atomic levels, the lower branch remains mainly and the upper mainly , with increasing admixture where their uncoupled energies approach.
The upper-right panel of the figure in part (a)(ii) compares the mixed curves with dashed unmixed curves. The mixing vanishes at both and , so those endpoints remain unchanged. If the unmixed curves approach or cross in the interior, the nonzero coupling produces an avoided crossing.

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