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UPSC Combined Geo-Scientist

Chemist

  • 3 descriptive papers
  • 200 marks each
  • 3 h per paper

Mains Paper II covers physical chemistry.

UPSC Combined Geo-Scientist, Mains · 2024 · Mains Paper II

Q1(o). Fluorescence rate constant of tryptophan

Question

The fluorescence quantum yield and observed fluorescence lifetime of tryptophan in water are ϕF,0 = 0.20 and τ₀ = 2.6 ns, respectively. Calculate the fluorescence rate constant, kF.

Answer in brief

kF = ϕF/τ₀ = 7.7 × 10⁷ s⁻¹ (radiative lifetime 13 ns).

Key points

  • S₁ decays by all paths together: τ₀ = 1/(kF + kIC + kISC + …), ϕF = kF/(kF + kIC + kISC + …) = kF τ₀.
  • kF = ϕF/τ₀ = 0.20/(2.6 × 10⁻⁹ s) = 7.7 × 10⁷ s⁻¹.
  • Radiative (natural) lifetime τrad = 1/kF = 13 ns; non-radiative knr = (1 − ϕF)/τ₀ = 3.1 × 10⁸ s⁻¹.
  • Tryptophan fluorescence (λem ≈ 350 nm) is the intrinsic probe of protein folding.

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(o), 2024 Mains Paper II: solution pages 17 and 18
Solution pages 17 and 18 of 37

Coversfluorescence quantum yieldfluorescence lifetimeradiative rate constanttryptophannon-radiative decay