UNSPECIFIED. (2004) Intracluster stereochemistry in van der Waals complexes: Steric effects in ultraviolet photodissociation of state-selected Ar-HOD/H2O. JOURNAL OF CHEMICAL PHYSICS, 120 (18). pp. 8443-8452. ISSN 0021-9606

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Abstract

High-resolution IR-UV multiple resonance methods are employed to elucidate the photodissociation dynamics of quantum state-selected Ar-HOD and Ar-H2O van der Waals clusters. A single mode pulsed OPO operating in the region of the OH second overtone is used to prepare individual rovibrational states that are selectively photodissociated at specific excimer wavelengths. Subsequent fluorescence excitation of the resulting OH (OD) fragments yields dynamical information on the photofragmentation event and any resulting intracluster collisions. This technique is used to characterize spectroscopically the Pi(1(01)), upsilon(OH) = 3 <--Sigma(0(00)), upsilon(OH) = 0 overtone band of the Ar-HOD complex with an origin at 10648.27 cm(-1). The effects of Ar complexation on the dissociation dynamics are inferred by comparison of the OD photofragment quantum state distributions resulting from dissociation of single rovibrational states of the complex with those from isolated HOD photodissociation. The important role played by the initial internal state of the complex is demonstrated by comparison of the current Ar-HOD data with previously published results for the Ar-H2O Sigma(0(00))\03(-)> state. We interpret the dramatic differences in the dynamics of the two systems as manifestations of the. nodal structure of the vibrational state in the parent complex and the way in which it governs the collision probability between the Ar atom and the escaping photofragments. (C) 2004 American Institute of Physics.

Item Type:	Journal Article
Subjects:	Q Science > QC Physics
Journal or Publication Title:	JOURNAL OF CHEMICAL PHYSICS
Publisher:	AMER INST PHYSICS
ISSN:	0021-9606
Date:	8 May 2004
Volume:	120
Number:	18
Number of Pages:	10
Page Range:	pp. 8443-8452
Identification Number:	10.1063/1.1697394
Publication Status:	Published
URI:	http://wrap.warwick.ac.uk/id/eprint/8443

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