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Related Experiment Video

Updated: Mar 15, 2026

Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
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Communication: Tunnelling splitting in the phosphine molecule.

Clara Sousa-Silva1, Jonathan Tennyson1, Sergey N Yurchenko1

  • 1Department of Physics and Astronomy, University College London, London WC1E 6BT, United Kingdom.

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|September 10, 2016
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Summary

Quantum tunneling in phosphine (PH3) molecules can be observed in near-infrared spectra. Variational nuclear motion calculations predict observable splittings in overtones of the ν2 bending mode, starting with 4ν2.

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Area of Science:

  • Quantum mechanics
  • Molecular spectroscopy
  • Computational chemistry

Background:

  • Tunneling through potential energy barriers is crucial in molecular spectroscopy.
  • The ammonia (NH3) doublet inspired searches for phosphine (PH3) analogs.
  • Higher energy barriers in PH3 have hindered observation of similar splittings.

Purpose of the Study:

  • To predict quantum tunneling splittings in phosphine.
  • To determine if these splittings are experimentally observable.
  • To identify spectral regions for potential observation.

Main Methods:

  • Full-dimensional, variational nuclear motion calculations.
  • Simulation of molecular spectra.
  • Analysis of splittings as a function of excitation energy.

Main Results:

  • Calculations predict observable tunneling splittings in phosphine.
  • These splittings are expected in the near-infrared region.
  • The 4ν2 overtone of the ν2 bending mode is a promising region for observation.

Conclusions:

  • Quantum tunneling effects in phosphine are theoretically predictable.
  • Experimental observation of phosphine splittings is feasible.
  • Near-infrared spectroscopy targeting ν2 bending overtones offers a pathway to detect these phenomena.