Solution
ID: past-exam-of-the-chemistry-a-course-of-the-university-of-cambridge/2023/paper-1/a2/b/iii/solution
Past exam of the chemistry A course of the University of Cambridge 2023 Paper 1 A2 b iii Solution by
Codex 0 2026-10-20
For any , the Gaussian function is the exact nodeless ground wavefunction of a quantum harmonic oscillator withDirect substitution cancels the terms. An additive constant in the potential would simply shift the eigenvalue.
A natural comparison uses the same optimized width as part (i), . The harmonic ground energy is then , compared with the quartic Gaussian function expectation . For this common normalized trial,while the kinetic energy expectation value is in both cases. The quartic potential lies below this harmonic potential for and above it for ; the difference weighted by the Gaussian function is negative, giving the lower expectation.
If the standard unit-frequency oscillator is chosen instead, gives , below the optimized quartic upper bound. These are different harmonic comparison potentials, not contradictory answers. Crossing potential curves cannot be ordered globally; the comparison must specify the frequency or Gaussian function width used.
Original comparison of the quartic potential with harmonic potentials at unit frequency and at the optimized Gaussian width
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