TY - JOUR
T1 - Energy transfer dynamics in the collision-induced dissociation of Al6 and Al13 clusters
AU - De Sainte Claire, Pascal
AU - Peslherbe, Gilles H.
AU - Hase, William L.
N1 - Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 1995
Y1 - 1995
N2 - Using a model analytic potential energy function developed for Aln clusters [J. Chem. Phys. 1987, 87, 2205] and a UMP2(fc)/6-31G* potential derived here for the Ar-Al interaction, classical trajectory simulations are performed to study collision-induced dissociation (CID) of Al6 and Al13 with argon. For the octahedral Al6 (Oh) cluster the CID threshold is ∼14 kcal/mol higher than the true threshold. This is because, near the threshold, there are no trajectories which transfer all the reactant relative translational energy to Al6 internal energy. For the planar Al6 (C2h) cluster, the CID threshold is closer to the true threshold. For the spherically shaped Al6 (Oh) and Al13 (D3d) clusters, T → V is the predominant energy transfer pathway. T → R energy transfer is important for the planar Al6 (C2h), Al13 (D2h), and Al13 (D6h) clusters. T → V energy transfer is enhanced as the cluster is softened (i.e., its vibrational frequencies lowered), the mass of the colliding atom is increased, and/or the relative velocity is increased. These effects are consistent with a previously derived impulsive model [J. Chem. Phys. 1970, 52, 5221], which says T → V energy transfer increases as the collisional adiabaticity parameter ξ is decreased.
AB - Using a model analytic potential energy function developed for Aln clusters [J. Chem. Phys. 1987, 87, 2205] and a UMP2(fc)/6-31G* potential derived here for the Ar-Al interaction, classical trajectory simulations are performed to study collision-induced dissociation (CID) of Al6 and Al13 with argon. For the octahedral Al6 (Oh) cluster the CID threshold is ∼14 kcal/mol higher than the true threshold. This is because, near the threshold, there are no trajectories which transfer all the reactant relative translational energy to Al6 internal energy. For the planar Al6 (C2h) cluster, the CID threshold is closer to the true threshold. For the spherically shaped Al6 (Oh) and Al13 (D3d) clusters, T → V is the predominant energy transfer pathway. T → R energy transfer is important for the planar Al6 (C2h), Al13 (D2h), and Al13 (D6h) clusters. T → V energy transfer is enhanced as the cluster is softened (i.e., its vibrational frequencies lowered), the mass of the colliding atom is increased, and/or the relative velocity is increased. These effects are consistent with a previously derived impulsive model [J. Chem. Phys. 1970, 52, 5221], which says T → V energy transfer increases as the collisional adiabaticity parameter ξ is decreased.
UR - http://www.scopus.com/inward/record.url?scp=0347240280&partnerID=8YFLogxK
U2 - 10.1021/j100020a043
DO - 10.1021/j100020a043
M3 - Article
AN - SCOPUS:0347240280
VL - 99
SP - 8147
EP - 8161
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
SN - 0022-3654
IS - 20
ER -