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

Transition state theory: variational formulation, dynamical corrections, and error estimates.

Eric Vanden-Eijnden1, Fabio A Tal

  • 1Courant Institute of Mathematical Sciences, New York University, New York, New York 10012, USA. eve2@cims.nyu.edu

The Journal of Chemical Physics
|November 19, 2005
PubMed
Summary
This summary is machine-generated.

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

Model-Free Learning of Probability Flows: Elucidating the Nonequilibrium Dynamics of Flocking.

Physical review letters·2025
Same author

Evolving Motility of Active Droplets Is Captured by a Self-Repelling Random Walk Model.

Physical review letters·2025
Same author

Unveiling the Phase Diagram and Reaction Paths of the Active Model B with the Deep Minimum Action Method.

Physical review letters·2024
Same author

Deep learning probability flows and entropy production rates in active matter.

Proceedings of the National Academy of Sciences of the United States of America·2024
Same author

Computing equilibrium free energies through a nonequilibrium quench.

The Journal of chemical physics·2024
Same author

Adaptive Monte Carlo augmented with normalizing flows.

Proceedings of the National Academy of Sciences of the United States of America·2022
Same journal

Anharmonic phonons via quantum thermal bath simulations.

The Journal of chemical physics·2026
Same journal

Quantum simulation of alignment dependent differential cross sections in co-propagating molecular beams at cold collision energies.

The Journal of chemical physics·2026
Same journal

Non-additive ion effects on the coil-globule equilibrium of a generic polymer in aqueous salt solutions.

The Journal of chemical physics·2026
Same journal

Insights into the unexpected small reduction of the temperature of maximum density of water by lithium chloride addition.

The Journal of chemical physics·2026
Same journal

Optical frequency comb double-resonance spectroscopy of the 9030-9175 cm-1 states of ethylene.

The Journal of chemical physics·2026
Same journal

Time reversal breaking of colloidal particles in cells.

The Journal of chemical physics·2026
See all related articles

This study revisits Transition State Theory (TST) and its advanced forms, like variational TST. It introduces methods for exact transition rate calculations and discusses optimizing the dividing surface for accurate dynamical corrections.

Area of Science:

  • Chemical Kinetics
  • Theoretical Chemistry
  • Statistical Mechanics

Background:

  • Transition State Theory (TST) is a fundamental concept for calculating reaction rates.
  • Existing methods often require approximations for dynamical corrections and optimal dividing surface selection.
  • Accurate computation of transition rates between metastable states is crucial in many chemical and physical processes.

Purpose of the Study:

  • To revisit and extend Transition State Theory (TST).
  • To develop exact methods for computing transition rates between predefined sets in phase space.
  • To derive criteria for optimal TST dividing surfaces and analyze the efficiency of dynamical corrections.

Main Methods:

  • Exact computation of mean transition frequencies between phase space partitions.

Related Experiment Videos

  • Derivation of exact and approximate criteria for optimal TST dividing surfaces.
  • Analysis of numerical error scaling for the transmission coefficient (kappaS).

    • Main Results:

    • Exact methods for calculating transition rates between metastable states are presented.
    • Criteria for minimizing recrossing rates and optimizing the TST dividing surface are derived.
    • Error analysis shows that efficient dynamical corrections require a sufficiently large transmission coefficient (kappaS) for the dividing surface.

    Conclusions:

    • Optimizing the TST dividing surface is essential for accurate and efficient dynamical corrections.
    • The efficiency of computing dynamical corrections depends critically on the transmission coefficient of the chosen dividing surface.
    • The study provides a framework for more precise calculations of chemical reaction rates and transitions between conformational states.