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Orientation and alignment depolarization in OH(X 2Pi)+Ar/He collisions.

Grant Paterson1, Sarantos Marinakis, Matthew L Costen

  • 1School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, United Kingdom.

The Journal of Chemical Physics
|December 3, 2008
PubMed
Summary

This study investigates the depolarization of hydroxyl radical (OH) rotational angular momentum during collisions with helium and argon. Results reveal differences in depolarization rates, suggesting attractive forces influence elastic depolarization in OH+Ar collisions.

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Area of Science:

  • Molecular collision dynamics
  • Quantum mechanics
  • Spectroscopy

Background:

  • Understanding molecular collisions is crucial for chemical kinetics and atmospheric science.
  • The hydroxyl radical (OH) is a key species in combustion and atmospheric chemistry.
  • Depolarization of rotational angular momentum provides insights into collision dynamics.

Purpose of the Study:

  • To investigate the depolarization of OH rotational angular momentum in collisions with He and Ar.
  • To differentiate between orientation and alignment depolarization mechanisms.
  • To test the accuracy of ab initio potential energy surfaces for OH-He collisions.

Main Methods:

  • Two-color polarization spectroscopy (PS) was employed to study OH depolarization.
  • Circularly and linearly polarized light were used to induce and probe orientation and alignment.
  • Exact, fully quantum-mechanical scattering calculations were performed on a new potential energy surface.

Main Results:

  • Depolarization rate constants (k(PS)) were measured for OH(X)+He and OH(X)+Ar collisions at 298 K.
  • k(dep) was found to be significantly higher for alignment than orientation in OH(X)+Ar collisions.
  • Calculated rate constants (k(RET), k(Lambda)) supported a substantial k(dep) contribution for OH(X)+Ar.

Conclusions:

  • The study highlights differences in elastic depolarization mechanisms between OH+Ar and OH+He collisions.
  • Attractive forces likely play a role in elastic depolarization for OH+Ar.
  • The findings provide a sensitive test for theoretical OH-He potential energy surfaces.