Conformational kinetics in liquid butane by nonequilibrium molecular dynamics
- 15 November 1987
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 87 (10), 5700-5708
- https://doi.org/10.1063/1.453545
Abstract
A new nonequilibrium molecular dynamics (NEMD) algorithm is used to calculate rate constants for trans–gauche isomerization in pure liquid butane. The new NEMD algorithm is based on macroscopic kinetic relaxation to equilibrium. The kinetic rate constant at T=292 K and ρ=0.583 g/ml is k=kF+kR =4.8×1010 s−1. The transition state theory rate constant is kTST =2.8×1011 s−1. The transmission coefficient is κ=0.17. Transition state theory overestimates the rate constant by a factor of 5.Keywords
This publication has 23 references indexed in Scilit:
- Rheology of n-alkanes by nonequilibrium molecular dynamicsThe Journal of Chemical Physics, 1987
- Molecular dynamics of the A+BC reaction in rare gas solutionThe Journal of Chemical Physics, 1986
- On determining reaction kinetics by molecular dynamics using absorbing barriersThe Journal of Physical Chemistry, 1985
- Isomerization dynamics and the transition to chaosThe Journal of Physical Chemistry, 1982
- Fluctuation expressions for fast thermal transport processes: Vortex viscosityPhysical Review A, 1982
- Stochastic molecular dynamics study of t r a n s–g a u c h e isomerization processes in simple chain moleculesThe Journal of Chemical Physics, 1980
- Riemann tensor theory of liquid state chain dynamicsThe Journal of Chemical Physics, 1980
- Time-Correlation Functions and Transport Coefficients in Statistical MechanicsAnnual Review of Physical Chemistry, 1965
- Statistical investigation of dissociation cross-sections for diatomsDiscussions of the Faraday Society, 1962
- Markoff Random Processes and the Statistical Mechanics of Time-Dependent Phenomena. II. Irreversible Processes in FluidsThe Journal of Chemical Physics, 1954