title: Transition state theory for solvated reactions beyond recrossing-free dividing surfaces.
abstract: The accuracy of rate constants calculated using transition state theory depends crucially on the correct identification of a recrossing-free dividing surface. We show here that it is possible to define such optimal dividing surface in systems with non-Markovian friction. However, a more direct approach to rate calculation is based on invariant manifolds and avoids the use of a dividing surface altogether, Using that method we obtain an explicit expression for the rate of crossing an anharmonic potential barrier. The excellent performance of our method is illustrated with an application to a realistic model for LiNC⇌LiCN isomerization.
authors.affiliation: Grupo de Sistemas Complejos, Escuela Técnica Superior de Ingeniería Agronómica, Alimentaria y de Biosistemas, Universidad Politécnica de Madrid, Avda. Complutense s/n 28040 Madrid, Spain.|Instituto de Ciencias Matemáticas (ICMAT), Cantoblanco, 28049 Madrid, Spain.
authors.forename: F
authors.initials: F
authors.lastname: Revuelta
authors.affiliation: Department of Mathematical Sciences, Loughborough University, Loughborough LE11 3TU, United Kingdom.
authors.forename: Thomas
authors.initials: T
authors.lastname: Bartsch
authors.affiliation: Centro de Investigaciones Energéticas Medioambientales y Tecnológicas, Avda. Complutense 40, 28040 Madrid, Spain.
authors.forename: P L
authors.initials: PL
authors.lastname: Garcia-Muller
authors.affiliation: Center for Computational Molecular Sciences and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0430, USA.
authors.forename: Rigoberto
authors.initials: R
authors.lastname: Hernandez
authors.affiliation: Grupo de Sistemas Complejos, Escuela Técnica Superior de Ingeniería Agronómica, Alimentaria y de Biosistemas, Universidad Politécnica de Madrid, Avda. Complutense s/n 28040 Madrid, Spain.
authors.forename: R M
authors.initials: RM
authors.lastname: Benito
authors.affiliation: Instituto de Ciencias Matemáticas (ICMAT), Cantoblanco, 28049 Madrid, Spain.|Departamento de Química, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain.
authors.forename: F
authors.initials: F
authors.lastname: Borondo