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Updated: Jan 22, 2026

Absolute Quantum Yield Measurement of Powder Samples
Published on: May 12, 2012
Activated quantum diffusion in a periodic potential above the crossover temperature
Reuven Ianconescu1, Eli Pollak1
1Chemical and Biological Physics Department, Weizmann Institute of Science, 76100 Rehovoth, Israel.
Abstract:
The recently improved Pollak, Grabert, and Hänggi (PGH) turnover theory for activated surface diffusion, including finite barrier effects, is extended and studied in the quantum domain. Analytic expressions are presented for the diffusion coefficient, escape rate, hopping distribution, and mean squared path length of particles initially trapped in one of the wells of a periodic potential, moving under the influence of a frictional and Gaussian random force. Tunneling is included by assuming incoherent quantum hopping at temperatures which are above the crossover temperature between deep tunneling and thermal activation. In the improved version of PGH theory as applied to activated surface diffusion, the potential governing the motion of the unstable mode remains periodic but with a scaled mass which increases with the friction strength. Application of the theory to a periodic cosine potential demonstrates that in the weak damping regime quantum diffusion is slower than classical diffusion due to above barrier quantum reflection which significantly shortens the mean squared path length as compared to the classical result. Finite barrier corrections increase this quantum suppression of diffusion or, equivalently, the inverse isotope effect, whereby the diffusion is faster for a heavier mass.
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