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Double Proton Transfer Across a Table: The Formic Acid Dimer-Fluorobenzene Complex.

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|August 27, 2021
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Double proton transfer tunneling in the formic acid dimer complex with fluorobenzene was studied. Fluorobenzene slows proton transfer but does not quench it, revealing quantum tunneling dynamics.

Keywords:
effective Hamiltonianhydrogen bondsproton transferquantum tunnelingrotational spectroscopy

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Area of Science:

  • Quantum mechanics
  • Chemical physics
  • Molecular spectroscopy

Background:

  • Proton transfer is a fundamental quantum mechanical process.
  • Understanding tunneling dynamics is crucial in chemistry and biology.

Purpose of the Study:

  • Investigate double proton transfer tunneling in a formic acid dimer-fluorobenzene complex.
  • Determine the effect of fluorobenzene on the tunneling dynamics.

Main Methods:

  • Rotational spectroscopy measurements.
  • Isotopic substitution experiments.
  • Quantum chemical calculations.

Main Results:

  • The complex forms a π-π stacked structure.
  • Double proton transfer tunneling was observed in the formic acid dimer.
  • Fluorobenzene decreased the tunneling splitting from 341(3) MHz to 267.608(1) MHz.
  • Fluorobenzene reorientation was observed during proton transfer.

Conclusions:

  • Fluorobenzene does not quench double proton transfer but modulates its rate.
  • The observed reduction in tunneling splitting is attributed to fluorobenzene's influence on the transfer motion.
  • Weakly bound complexes can exhibit complex quantum dynamics.