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UPSC Civil Services (Mains)

Chemistry optional

  • 2 papers
  • 250 marks each
  • 3 h per paper
  • 5 of 8 questions, Q1 and Q5 compulsory

Paper I covers physical and inorganic chemistry.

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.

Model answer to Q1(a), 2021 Paper I: solution pages 1 and 2
Solution pages 1 and 2 of 59
Model answer to Q1(a), 2021 Paper I: solution pages 3 and 4
Solution pages 3 and 4 of 59

Coversparticle in a boxexpectation valueground state wave functionposition operatorcorrespondence principle