@article { ISI:A1994NT52100037,
	title = {SOLVATION EFFECTS ON ASSOCIATION REACTIONS IN MICROCLUSTERS - CLASSICAL TRAJECTORY STUDY OF H+CL(AR)(N)},
	journal = {JOURNAL OF CHEMICAL PHYSICS},
	volume = {101},
	year = {1994},
	month = {JUL 1},
	pages = {343-355},
	abstract = {The role of solvent effects in association reactions is studied in atom-cluster collisions. Classical trajectory studies of the systems H+Cl(Ar)(n) (n = 1,12) are used to investigate the influence of size, structure, and internal energy of the {\textquoteleft}{\textquoteright}microsolvation{\textquoteright}{\textquoteright} on the H+Cl association reaction. The following effects of solvating the chlorine in an Ar, cluster are found. (1) In the H+ClAr system there is a large {\textquoteleft}{\textquoteright}third body{\textquoteright}{\textquoteright} effect. The single solvent atom stabilizes the newly formed HCl molecule by removing some of its excess energy. The cross section found at low energies is a substantial fraction of the gas-kinetic cross section. The molecule is produced in highly excited vibrational-rotational states. (2) Some production of long-lived HCl...Ar complexes, with lifetimes of 1 ps and larger, is found for the H+ClAr collisions. Weak coupling stemming from the geometry of the cluster is the cause for long life times. These resonance states decay into HCl+Ar. (3) At low collision energy (E = 10 kJ/mol) for H+Cl(Ar)(12), the H+Cl association shows a sharp threshold effect with cluster temperature. For temperatures T greater than or equal to 45 K the cluster is liquidlike, and the reaction probability is high. For T less than or equal to 40 K the cluster is solidlike, and there is no reactivity. This suggests the potential use of reactions as a signature for the meltinglike transition in clusters. (4) At high collision energies (E = 100 kJ/mol) H atoms can penetrate also the solidlike Cl(Ar)(12) cluster. At this energy, the solid-liquid phase change is found not to increase the reaction probability.},
	issn = {0021-9606},
	doi = {10.1063/1.468141},
	author = {Schmidt, B. and Gerber, R. B.}
}
