TY - JOUR

T1 - Lyapunov exponents for the intramolecular motion of the Cl--CH3Br complex

AU - Wang, Haobin

AU - Hase, William L.

N1 - Copyright:
Copyright 2020 Elsevier B.V., All rights reserved.

PY - 1997

Y1 - 1997

N2 - The intramolecular dynamics of Cl-- - -CH3Br complexes is studied at an energy approximately equal to the average thermal energy of complexes formed by Cl- + CH3Br association at 300 K. Lyapunov exponents are calculated for different mode excitations of the Cl-- - -CH3Br complex. Without zero-point energy added to the complex, a number of the mode excitations have zero Lyapunov exponents and, thus, regular motion. The Lyapunov exponents are positive and the motion is chaotic for all mode excitations with zero-point energy added. However, the latter Lyapunov exponents are sufficiently small that the time required to form a microcanonical ensemble of Cl-- - -CH3Br states is much longer than the RRKM lifetime of the complex. Thus, non-RRKM unimolecular dynamics is expected for the Cl-- - -CH3Br complex as found in previous trajectory simulations.

AB - The intramolecular dynamics of Cl-- - -CH3Br complexes is studied at an energy approximately equal to the average thermal energy of complexes formed by Cl- + CH3Br association at 300 K. Lyapunov exponents are calculated for different mode excitations of the Cl-- - -CH3Br complex. Without zero-point energy added to the complex, a number of the mode excitations have zero Lyapunov exponents and, thus, regular motion. The Lyapunov exponents are positive and the motion is chaotic for all mode excitations with zero-point energy added. However, the latter Lyapunov exponents are sufficiently small that the time required to form a microcanonical ensemble of Cl-- - -CH3Br states is much longer than the RRKM lifetime of the complex. Thus, non-RRKM unimolecular dynamics is expected for the Cl-- - -CH3Br complex as found in previous trajectory simulations.

UR - http://www.scopus.com/inward/record.url?scp=4243429193&partnerID=8YFLogxK

U2 - 10.1016/s0168-1176(97)00102-x

DO - 10.1016/s0168-1176(97)00102-x

M3 - Article

AN - SCOPUS:4243429193

VL - 167-168

SP - 573

EP - 585

JO - International Journal of Mass Spectrometry and Ion Processes

JF - International Journal of Mass Spectrometry and Ion Processes

SN - 0168-1176

ER -