Observatorio de I+D+i UPM

Memorias de investigación
Artículos en revistas:
The geometry of transition states: How invariant manifolds determine reaction rates
Año:2018
Áreas de investigación
  • Algebra,
  • Geometría,
  • Mecánica,
  • Química,
  • Química física,
  • Química cuántica,
  • Dinámica molecular,
  • Fisica y ciencias del espacio,
  • Fisica am -- fisica atomica y molecular,
  • Fisica st -- mecanica estadistica,
  • Fisica mp -- fisica matematica,
  • Fisica cs -- sistemas complejos
Datos
Descripción
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.
Internacional
Si
JCR del ISI
No
Título de la revista
Chaotic Modeling and Simulation (CMSIM)
ISSN
2241-0503
Factor de impacto JCR
Información de impacto
Volumen
3
DOI
10.1063/1.4997571
Número de revista
Desde la página
305
Hasta la página
318
Mes
JULIO
Ranking
Esta actividad pertenece a memorias de investigación
Participantes
  • Autor: Fabio Revuelta Peña (UPM)
  • Autor: Thomas Bartsch (Loghborough University)
  • Autor: Florentino Borondo (Universidad Autónoma de Madrid)
  • Autor: Rosa Maria Benito Zafrilla (UPM)
Grupos de investigación, Departamentos, Centros e Institutos de I+D+i relacionados
  • Creador: Departamento: Ingeniería Agroforestal
S2i 2021 Observatorio de investigación @ UPM con la colaboración del Consejo Social UPM
Cofinanciación del MINECO en el marco del Programa INNCIDE 2011 (OTR-2011-0236)
Cofinanciación del MINECO en el marco del Programa INNPACTO (IPT-020000-2010-22)