Table of Contents
Laser Chemistry
Volume 15, Issue 2-4, Pages 209-220

The Importance of Electron Transfer Mechanism in Reactions of Neutral Transition Metal Atoms

1Department of Material Science, Himeji Institute of Technology, 1479-1 Kanaji, Kamigori, Hyogo 678-12, Japan
2Department of Chemistry, Northwestern University, Evanston, Illinois, USA

Received 8 April 1994

Copyright © 1995 Hindawi Publishing Corporation. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


Reaction kinetics of ground, Ti(a3F) and V(a4F), and excited, Ti(a5F) and V(a6D), states atoms with some simple molecules have been studied by a discharge-flow tube technique. Laser-induced fluorescence (LIF) was used to determine the concentration of the metal atoms as a function of the flow rate of the reactant molecule to obtain effective bimolecular rate constants. The rate constants of reactions with OX (X = O, N, N2) and H2S show strong inverse correlation with effective ionization potentials (I.P.-Eel, where I.P. and Eel are ionization potential and electronic energy of metal atom) of the metal atoms. This result suggests that the electron transfer mechanism plays an important role in these reactions. The large rate constants for electronic excited states can be explained by the crossing between ionic and flat neutral potential energy surfaces. The inefficient reaction rates measured for ground states can be explained by the repulsive nature of 4s2 configuration which can result in a potential barrier.