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Spin-orbit interaction mediated molecular dissociation.

E Kokkonen1, T Löytynoja1, K Jänkälä1

  • 1Department of Physics, University of Oulu, Box 3000, 90014 Oulu, Finland.

The Journal of Chemical Physics
|May 17, 2014
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Summary

Spin-orbit interaction significantly impacts mercury(II) bromide (HgBr2) photofragmentation. Researchers observed distinct fragmentation patterns due to spin-orbit coupling in Hg 5d photoionization, confirmed by advanced spectroscopy and theoretical analysis.

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Area of Science:

  • Atomic and Molecular Physics
  • Chemical Physics
  • Quantum Chemistry

Background:

  • The mercury(II) bromide (HgBr2) molecule is a key system for studying electronic structure and photochemistry.
  • Spin-orbit interaction plays a crucial role in the electronic properties and dissociation dynamics of heavy-atom molecules.
  • Understanding photoionization and subsequent fragmentation is essential for predicting molecular behavior under irradiation.

Purpose of the Study:

  • To investigate the influence of spin-orbit interaction on the photofragmentation of mercury(II) bromide (HgBr2).
  • To analyze the changes in fragmentation patterns arising from different spin-orbit components of Hg 5d photoionization.
  • To explore the effects of molecular-field splitting within these spin-orbit components on dissociation.

Main Methods:

  • Utilizing synchrotron radiation for high-energy photon excitation.
  • Employing photoelectron-photoion coincidence spectroscopy to correlate photoionization events with fragment ions.
  • Performing relativistic ab initio calculations to interpret the experimental photoelectron spectrum.

Main Results:

  • Observed distinct differences in photofragmentation pathways between the two spin-orbit components of Hg 5d photoionization.
  • Identified variations in fragmentation within the molecular-field-splitted levels of these spin-orbit components.
  • Relativistic ab initio analysis provided theoretical support for the experimental observations.

Conclusions:

  • Spin-orbit interaction is a critical factor governing the photofragmentation dynamics of HgBr2.
  • The study elucidates the complex interplay between electronic structure, spin-orbit coupling, and molecular dissociation.
  • This research contributes to a deeper understanding of photoionization processes in heavy-element molecules.