TY - JOUR

T1 - A comparison of classical trajectory and statistical unimolecular rate theory calculations of Al3 decomposition

AU - Peslherbe, Gilles H.

AU - Hase, William L.

N1 - Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.

PY - 1994

Y1 - 1994

N2 - Classical trajectories are used to simulate the dissociation of microcanonical ensembles of Al3 clusters with 0.25-2.00 kcal/mol energy in excess of the dissociation threshold. Unimolecular lifetime distributions for the ensembles are in accord with the random lifetime prescription of Rice-Ramsperger-Kassel-Marcus (RRKM) theory and Al3 is identified as an intrinsic RRKM molecule. Unimolecular rate constants determined from the trajectories are compared with the predictions of variational RRKM theory with harmonic vibrator and flexible transition state models, phase space theory (PST), and the orbiting transition state model of phase space theory (OTS/PST). The flexible RRKM model, PST, and OTS/PST give Al2- - -Al transition state sums of state which agree to within 1%. The harmonic vibrator RRKM model gives a sum of states which varies from only 40% to 10% larger as the excess energy is increased from 0.25 to 2.0 kcal/mol. Adiabatic switching and direct integration of the phase integral are used to determine the reactant Al3 anharmonic density of states. For the energies considered in this work, anharmonicity determined by adiabatic switching increases the Al3 density of states from the harmonic value by a factor of 2.5-2.9. The anharmonic density of states determined by solving the phase integral depends on where the reactant/product phase space boundary is positioned. Placing it at the vibrator transition state gives an anharmonic density of states nearly the same as that determined by adiabatic switching, while placing it at the looser flexible transition state gives a density of states 35% larger at the highest energy. Using this latter anharmonic density of states gives OTS/PST and flexible RRKM Unimolecular rate constants which agree with the trajectory results to within 25% at the lowest energy and 10% at the highest energy. Product energy partitioning distributions determined from the trajectories are compared with the predictions of PST, OTS/PST, and the Engelking model. Both OTS/PST and PST give product energy partitioning distributions which are in near quantitative agreement with the trajectory results.

AB - Classical trajectories are used to simulate the dissociation of microcanonical ensembles of Al3 clusters with 0.25-2.00 kcal/mol energy in excess of the dissociation threshold. Unimolecular lifetime distributions for the ensembles are in accord with the random lifetime prescription of Rice-Ramsperger-Kassel-Marcus (RRKM) theory and Al3 is identified as an intrinsic RRKM molecule. Unimolecular rate constants determined from the trajectories are compared with the predictions of variational RRKM theory with harmonic vibrator and flexible transition state models, phase space theory (PST), and the orbiting transition state model of phase space theory (OTS/PST). The flexible RRKM model, PST, and OTS/PST give Al2- - -Al transition state sums of state which agree to within 1%. The harmonic vibrator RRKM model gives a sum of states which varies from only 40% to 10% larger as the excess energy is increased from 0.25 to 2.0 kcal/mol. Adiabatic switching and direct integration of the phase integral are used to determine the reactant Al3 anharmonic density of states. For the energies considered in this work, anharmonicity determined by adiabatic switching increases the Al3 density of states from the harmonic value by a factor of 2.5-2.9. The anharmonic density of states determined by solving the phase integral depends on where the reactant/product phase space boundary is positioned. Placing it at the vibrator transition state gives an anharmonic density of states nearly the same as that determined by adiabatic switching, while placing it at the looser flexible transition state gives a density of states 35% larger at the highest energy. Using this latter anharmonic density of states gives OTS/PST and flexible RRKM Unimolecular rate constants which agree with the trajectory results to within 25% at the lowest energy and 10% at the highest energy. Product energy partitioning distributions determined from the trajectories are compared with the predictions of PST, OTS/PST, and the Engelking model. Both OTS/PST and PST give product energy partitioning distributions which are in near quantitative agreement with the trajectory results.

UR - http://www.scopus.com/inward/record.url?scp=33847017994&partnerID=8YFLogxK

U2 - 10.1063/1.468114

DO - 10.1063/1.468114

M3 - Article

AN - SCOPUS:33847017994

VL - 101

SP - 8535

EP - 8553

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

SN - 0021-9606

IS - 10

ER -