Jove
Visualize
Contact Us
JoVE
x logofacebook logolinkedin logoyoutube logo
ABOUT JoVE
OverviewLeadershipBlogJoVE Help Center
AUTHORS
Publishing ProcessEditorial BoardScope & PoliciesPeer ReviewFAQSubmit
LIBRARIANS
TestimonialsSubscriptionsAccessResourcesLibrary Advisory BoardFAQ
RESEARCH
JoVE JournalMethods CollectionsJoVE Encyclopedia of ExperimentsArchive
EDUCATION
JoVE CoreJoVE BusinessJoVE Science EducationJoVE Lab ManualFaculty Resource CenterFaculty Site
Terms & Conditions of Use
Privacy Policy
Policies

Related Experiment Videos

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.

Related Concept Videos

You might also read

Related Articles

Articles linked to this work by shared authors, journal, and citation graph.

Sort by
Same author

Quantum Kramers model: Corrections to the linear response theory for continuous bath spectrum.

Physical review. Eยท2017
See all related articles

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.

Related Experiment Videos

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.