Observatorio de I+D+i UPM

Memorias de investigación
Research Publications in journals:
Transition state theory for activated systems with driven anharmonic barriers
Year:2017
Research Areas
  • Physics chemical and mathematical
Information
Abstract
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.
International
Si
JCR
Si
Title
Journal of Chemical Physics
ISBN
0021-9606
Impact factor JCR
2,965
Impact info
Volume
147
10.1063/1.4997571
Journal number
From page
074104
To page
074104
Month
SIN MES
Ranking
Participants
  • 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)
Research Group, Departaments and Institutes related
  • Creador: Grupo de Investigación: Grupo de Sistemas Complejos
  • Departamento: Ingeniería Agroforestal
S2i 2019 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)