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Eyring equation and fluctuation-dissipation far away from equilibrium.

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Area of Science:

  • Theoretical Chemistry
  • Chemical Dynamics
  • Statistical Mechanics

Background:

  • Managing external forces and non-equilibrium environments is crucial for theoretical chemistry.
  • Generalizing transition state theory for non-equilibrium situations remains a key challenge.

Purpose of the Study:

  • To generalize Eyring's equation for systems far from equilibrium.
  • To develop a theoretical framework for chemical processes influenced by external forces.

Main Methods:

  • Utilizing generalized Langevin dynamics to analyze coupled fast and slow dynamic variables.
  • Defining an effective thermal energy (temperature) arising from dynamic variable coupling.
  • Restoring effective adiabatic timescale separation via effective thermal energy.

Main Results:

  • The proposed method allows for the generalization of Eyring's equation.
  • An effective thermal energy accounts for the non-equilibration of fast degrees of freedom.
  • Renormalization of the generalized fluctuation-dissipation theorem is achieved.

Conclusions:

  • The developed approach enables the study of chemical systems far from equilibrium.
  • Eyring's equation is successfully generalized to include the effects of strong external forces.
  • This work provides a new avenue for theoretical chemistry research in non-equilibrium systems.