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Dissipative curve crossing problem. I. High-barrier crossing.

Ilya Rips1

  • 1Department of Sciences, Holon Academic Institute of Technology, Holon 58102, Israel. rips@hait.ac.il

The Journal of Chemical Physics
|September 9, 2004
PubMed
Summary

This study extends variational transition state theory to calculate radiationless transition rates for asymmetric crossings. Findings reveal how crossing asymmetry and dissipation strength impact transition dynamics in normal and inverted regions.

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Area of Science:

  • Chemical Physics
  • Theoretical Chemistry
  • Quantum Dynamics

Background:

  • Radiationless transitions are crucial in chemical reactions and molecular processes.
  • Understanding these transitions requires accurate theoretical models, especially for complex systems with high energy barriers.

Purpose of the Study:

  • To extend the diabatic variational transition state theory (DVTT) for calculating radiationless transition rates.
  • To investigate the influence of crossing asymmetry and dissipation strength on these rates for normal and inverted crossings.

Main Methods:

  • Utilized an extended variational approach based on DVTT optimization.
  • Employed a scaling argument to derive an analytic expression for renormalized frequency under Ohmic dissipation.
  • Analyzed the impact of crossing asymmetry on physical parameters and transition rates.

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Main Results:

  • Derived an analytic expression for renormalized frequency dependent on asymmetry and dissipation strength (Ohmic).
  • Observed that the effective adiabaticity parameter changes with asymmetry differently in normal and inverted regions.
  • Demonstrated qualitatively different radiationless transition rate behavior in normal and inverted regions under strong dissipation (Smoluchowski limit).
  • Found stretched exponential decay in the inverted region as a function of dissipation strength, indicating adiabatic suppression.

Conclusions:

  • The DVTT approach provides insights into radiationless transitions for asymmetric crossings.
  • Crossing asymmetry significantly affects transition dynamics, with distinct behaviors in normal and inverted regimes.
  • The model's accuracy is limited by increasing asymmetry in the normal region and decreasing asymmetry in the inverted region, breaking down in activationless cases.