Memorias de investigación
Research Publications in journals:
The geometry of transition states: How invariant manifolds determine reaction rates
Year:2018

Research Areas
  • Algebra,
  • Geometry,
  • Mechanics,
  • Chemistry,
  • Physic chemistry,
  • Quantum chemistry,
  • Molecular dynamic,
  • Physics & space science,
  • Physics - Atomic and molecular physics,
  • Physics - Statistical mechanics,
  • Physics - Mathematical physics,
  • Physics - Complex systems

Information
Abstract
recrossings and approximate rates because it relies on a fixed dividing surface. We develop both per- turbative and numerical methods for the computation of a time-dependent recrossing-free dividing surface for a model anharmonic system in a solvated environment that interacts strongly with an oscil- latory external field. We extend our previous work, which relied either on a harmonic approximation or on periodic force driving. We demonstrate that the reaction rate, expressed as the long-time flux of reactive trajectories, can be extracted directly from the stability exponents, namely, Lyapunov expo- nents, of the moving dividing surface. Comparison to numerical results demonstrates the accuracy and robustness of this approach for the computation of optimal (recrossing-free) dividing surfaces and reaction rates in systems with Markovian solvation forces. The resulting reaction rates are in strong agreement with those determined from the long-time flux of reactive trajectories.Over the last years, a new geometrical perspective on transition state theory has been developed that provides a deeper insight on the reaction mechanisms of chemical systems. This new methodology is based on the identification of the invariant structures that organize the dynamics at the top of the energetic barrier that separates reactants and products. Moreover, it has allowed to solve, or at least circumvent, the recrossing-free problem in rate calculations. In this paper, we will discuss which kind of objects determine the reaction dynamics in the presence of dilute, dense and condensed phase baths.
International
Si
JCR
No
Title
Chaotic Modeling and Simulation (CMSIM)
ISBN
2241-0503
Impact factor JCR
Impact info
Volume
3
10.1063/1.4997571
Journal number
From page
305
To page
318
Month
JULIO
Ranking
Participants

Research Group, Departaments and Institutes related
  • Creador: Departamento: Ingeniería Agroforestal