On leave from Department of Chemistry University of Ljubljana Ljubljana Slovenia.
Internal energy deposition in doubly charged tungsten hexacarbonyl on charge exchange at high energy with atomic and molecular targets
Version of Record online: 7 APR 2005
Copyright © 1992 John Wiley & Sons, Ltd.
Organic Mass Spectrometry
Volume 27, Issue 7, pages 769–776, July 1992
How to Cite
Susič, R., Lu, L., Riederer, D. E., Žigon, D., Cooks, R. G. and Ast, T. (1992), Internal energy deposition in doubly charged tungsten hexacarbonyl on charge exchange at high energy with atomic and molecular targets. Org. Mass Spectrom., 27: 769–776. doi: 10.1002/oms.1210270702
- Issue online: 7 APR 2005
- Version of Record online: 7 APR 2005
- Manuscript Revised: 23 MAR 1992
- Manuscript Accepted: 23 MAR 1992
- Manuscript Received: 28 JAN 1992
Charge exchange of W(CO) in the course of 7 keV collisions with various targets results in singly charged ions which are highly internally excited. The distribution of internal energies estimated by the degree to which consecutive fragmentations by CO loss occur is broad and includes very high energies (up to 15 eV). This result is inconsistent with exclusive operation of long-range electron transfer e.g. by either a curve crossing or Demkov mechanism; rather it suggests that direct excitation to a high-energy repulsive state of the products also occurs perhaps by an electronic excitation mechanism. The nature of the internal energy distribution suggests mechanistic analogies with simple collisional activation. Different target gases give rise to different average internal energy depositions monatomics and diatomics yielding higher energy depositions than do polyatomic targets. There is an approximate correlation between energy deposition and target ionization energy which is consistent with the proposed excitation mechanism considering the shapes of the potential energy surfaces. When the detailed internal energy distributions are compared characteristic differences are seen for individual targets. The efficiencies of the various targets at producing charge exchange were also compared. Large differences were found with the polyatomic targets having the greatest efficiencies. In addition a rough correlation was observed between the extent of charge exchange and target ionization energy and this is interpreted in terms of greater contributions from the long-range electron transfer process for targets of lower ionization energy. All the results are also consistent with contributons from more violent collisions which involve electron transfer at relatively small internuclear distances where the shapes of the potential surfaces are strongly dependent on distance.