UPSC Civil Services (Mains), Chemistry optional · 2021 · Paper I
Q1(a). Expectation value of position in the ground state of a box
Question
Calculate ⟨x⟩, the expectation value of position of a particle, in the ground state of one-dimensional box having length from 0 to l.
Answer in brief
⟨x⟩ = ∫₀ˡ ψ₁ x ψ₁ dx = l/2: the average position in the ground state is the centre of the box.
Key points
- Inside the box the normalised wave functions are ψₙ = √(2/l) sin(nπx/l); the ground state is n = 1.
- The expectation value is ⟨A⟩ = ∫ ψ* Â ψ dτ, and the position operator is multiplication by x.
- Using sin²θ = ½(1 − cos 2θ), the cosine integral vanishes over one complete wave, leaving ⟨x⟩ = (1/l)(l²/2) = l/2.
- Symmetry: ψ² is the same at x and at l − x, so ⟨x⟩ = l/2 in every state, whatever the value of n.
- ⟨x⟩ is the mean of many measurements, not where the particle sits; the spread is Δx = 0.181 l.
The full model answer
As written for the answer booklet: the diagram carries the working, the lines stay short. Read here only; it is not offered as a download.


Topic notes: particle in a one-dimensional box, with derivations, figures and every PYQ →
Coversparticle in a boxexpectation valueground state wave functionposition operatorcorrespondence principle
All parts of Question 1
- 1(a) Expectation value of position in the ground state of a box10 marks
- 1(b) Born–Haber cycle: can NaCl₂ form?10 marks
- 1(c) Rubber band: change of length on heating10 marks
- 1(d) Vapour pressure of water at 100 °C from its value at 95 °C10 marks
- 1(e) Electrochemical series and its significance10 marks