Details of Grant 

EPSRC Reference:	GR/S86914/01
Title:	Photodissociation dynamics at the gas-liquid interface
Principal Investigator:	Ellis, Professor A
Other Investigators:
Researcher Co-Investigators:
Project Partners:
Department:	Chemistry
Organisation:	University of Leicester
Scheme:	Standard Research (Pre-FEC)
Starts:	10 January 2005	Ends:	09 January 2008	Value (£):	209,572
EPSRC Research Topic Classifications:	Gas & Solution Phase Reactions Instrumentation Eng. & Dev. Surfaces & Interfaces
EPSRC Industrial Sector Classifications:	Chemicals Environment
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Panel History:
Summary on Grant Application Form
Physical chemists have long been interested in a detailed understanding of chemical reactions at the molecular level. Photochemical reactions are particularly attractive because the reactant part of the chemistry is largely under control, and the dynamics of gas phase photochemical reactions in particular have been, and continue to be, extensively studied. Photochemical reactions at gas-solid interfaces have also been subjected to many detailed studies, since high vacuum conditions can be achieved and product molecules ejected into the vacuum can therefore be probed using sensitive techniques such as mass spectrometry or laser spectroscopy. The distribution of energy amongst the gas phase product molecules provides important information about the dynamics of the reaction at the surface.Comparable experiments for gas-liquid interfaces have been deterred by the high vapour pressures of common liquids, such as water. To date the only reported work has been restricted to very low vapour pressure liquids. In this proposal we describe a new approach for studying photodissociation dynamics at the gas-liquid interface. This will enable, for the first time, investigation of the photodissociation of molecules at the surface of volatile liquids. Our technique will employ a liquid microjet, a narrow filament of liquid formed inside a high vacuum chamber. Product molecules ejected into the gas phase by laser photodissociation at the liquid surface will be detected by laser-induced fluorescence spectroscopy and both their translational and internal energy state distributions will be determined.An understanding of photodissociation at gas-liquid interfaces poses some special challenges. The surface region of a liquid may have substantially different properties from the bulk, including composition, density, effective dielectric constant, and a disrupted hydrogen bonding network. The cage effect of the surrounding solvent may therefore also differ from the bulk. In this work we will explore such factors by focussing on the photodissociation reactions of H202, HOCI, and ICN at the surface of water. The energy distributions of the photoproducts ejected into the gas phase will be measured and a comparison of the findings for these three systems, coupled with information from molecular dynamics simulations performed elsewhere, will be used to extract the first detailed information on the dynamics of photochemical reactions of solutes at the surface of liquid water.
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Organisation Website:	http://www.le.ac.uk