title: The role of the CN vibration in the activated dynamics of LiNC<−>LiCN isomerization in an argon solvent at high temperatures.
abstract: The isomerization between CN-Li and Li-CN in an argon bath provides a paradigmatic example of a reaction in a solvent with tunable coupling. In previous work, we found that the rates exhibited a turnover with the density of the argon bath in the limit that the CN bond was held fixed [P. L. Garcia-Muller, R. Hernandez, R. M. Benito, and F. Borondo, J. Chem. Phys. 137, 204301 (2012)]. Here, we report the effect of the CN bond vibration on the dynamics and the persistence of the turnover. As hypothesized earlier, the CN bond is indeed weakly coupled with the reaction path despite the presence of the argon cage.
authors.affiliation: Centro de Investigaciones Energéticas Medioambientales y Tecnológicas, Avda. Complutense 40, 28040 Madrid, Spain.
authors.forename: Pablo 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 30332-0400, USA.
authors.forename: Rigoberto
authors.initials: R
authors.lastname: Hernandez
authors.affiliation: Grupo de Sistemas Complejos, Universidad Politécnica de Madrid, 28040 Madrid, Spain and Departamento de Física y Mecánica, Escuela Técnica Superior de Ingenieros Agrónomos, Universidad Politécnica de Madrid, 28040 Madrid, Spain.
authors.forename: R M
authors.initials: RM
authors.lastname: Benito
authors.affiliation: Departamento de Química, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain and Instituto de Ciencias Matemáticas (ICMAT), Cantoblanco, 28049 Madrid, Spain.
authors.forename: F
authors.initials: F
authors.lastname: Borondo