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Ponencias en congresos:
Transition state theory for activated systems with driven anharmonic barriers
Año:2018
Áreas de investigación
  • Física química y matemáticas
Datos
Descripción
Classical transition state theory has been extended to address chemical reactions across barriers that are driven and anharmonic. This resolves a challenge to the naive theory that necessarily leads to recrossings and approximate rates because it relies on a fixed dividing surface. We develop both perturbative 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 oscillatory 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 exponents, 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.
Internacional
Si
Nombre congreso
TraX International Conference 2018 [http://www.gsc.upm.es/trax2018/]
Tipo de participación
960
Lugar del congreso
Cantoblanco, Madrid (Spain)
Revisores
Si
ISBN o ISSN
CDP08UPM
DOI
Fecha inicio congreso
09/05/2018
Fecha fin congreso
10/05/2018
Desde la página
42
Hasta la página
42
Título de las actas
TraX International Conference 2018. Book of Abstracts [http://www.gsc.upm.es/trax2018/trax2018.pdf]
Esta actividad pertenece a memorias de investigación
Participantes
  • Autor: Fabio Revuelta Peña (UPM)
  • Autor: Galen Craven (University of Pennsylvania, USA)
  • Autor: Thomas Bartsch (Loughborough University, UK)
  • Autor: Florentino Borondo Rodríguez (Universidad Autónoma de Madrid)
  • Autor: Rosa Maria Benito Zafrilla (UPM)
  • Autor: Rigoberto Hernández (Johns Hopkins University, USA)
Grupos de investigación, Departamentos, Centros e Institutos de I+D+i relacionados
  • Creador: Grupo de Investigación: Grupo de Sistemas Complejos
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