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Dissipation enhanced vibrational sensing in an olfactory molecular switch.

Agata Chęcińska1, Felix A Pollock2, Libby Heaney1

  • 1Centre for Quantum Technologies, National University of Singapore, Singapore 117543, Singapore.

The Journal of Chemical Physics
|January 17, 2015
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Summary

Dissipation enhances molecular switch sensitivity and selectivity for odorant detection. This study shows that environmental details and strong dissipation are crucial for accurate modeling, unlike simpler semiclassical methods.

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Area of Science:

  • Physical Chemistry
  • Chemical Physics
  • Molecular Biophysics

Background:

  • Olfactory mechanisms involve vibrationally activated molecular switches.
  • Electron transport in donor-acceptor systems is influenced by vibrational modes and environment.

Purpose of the Study:

  • Investigate electron transport in a donor-acceptor pair coupled to a vibrational mode.
  • Analyze the dynamics of electronic and vibrational degrees of freedom beyond semiclassical approximations.
  • Evaluate the role of dissipation in molecular switch function and sensitivity.

Main Methods:

  • Derivation of a polaron master equation.
  • Study of electronic and vibrational dynamics.
  • Comparison with semiclassical (Marcus-Jortner) rate analyses.

Main Results:

  • Semiclassical methods fail to capture dynamics without explicit vibrational mode dissipation.
  • Strong dissipation on the odorant vibrational mode enables exponential electron transfer.
  • Dissipation significantly enhances molecular switch discrimination and sensitivity to vibrational frequency.
  • Environmental details critically alter molecular switch sensitivity and frequency resolution.

Conclusions:

  • Dissipation constructively facilitates sensitive and selective molecular switch operation.
  • Semiclassical rate equations are inadequate for analyzing molecular switch behavior across various parameters.
  • Environmental spectral details play a crucial role in molecular switch performance.