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Memorias de investigación
Artículos en revistas:
Transition state theory for activated systems with driven anharmonic barriers
Año:2017
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
JCR del ISI
Si
Título de la revista
Journal of Chemical Physics
ISSN
0021-9606
Factor de impacto JCR
2,965
Información de impacto
Volumen
147
DOI
10.1063/1.4997571
Número de revista
Desde la página
074104
Hasta la página
074104
Mes
SIN MES
Ranking
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Participantes
  • Autor: Fabio Revuelta Peña (UPM)
  • Autor: Galen T. Craven (University of Pennsylvania)
  • Autor: Thomas Bartsch (Loghborough University)
  • Autor: Florentino Borondo (Universidad Autónoma de Madrid)
  • Autor: Rosa Maria Benito Zafrilla (UPM)
  • Autor: Rigoberto Hernandez (Johns Hopkins Universit)
Grupos de investigación, Departamentos, Centros e Institutos de I+D+i relacionados
  • Creador: Grupo de Investigación: Grupo de Sistemas Complejos
  • Departamento: Ingeniería Agroforestal
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