Ion-molecule reaction dynamics: Velocity map imaging studies of N(+) and O(+) with CD3OD

The Journal of Chemical Physics
Linsen Pei, James M Farrar

Abstract

We present a study of the charge transfer reactions of the atomic ions N(+)and O(+) with methanol in the collision energy range from ∼2 to 4 eV. Charge transfer is driven primarily by energy resonance, although the widths of the product kinetic energy distributions suggest that significant interchange between relative translation and product vibration occurs. Charge transfer with CD3OD is more exoergic for N(+), and the nascent parent ion products appear to be formed in excited B̃ and C̃ electronic states, and fragment to CD2OD(+) by internal conversion and vibrational relaxation to the ground electronic state. The internal excitation imparted to the parent ion is sufficient to result in loss of one or two D atoms from the carbon atom. The less exoergic charge transfer reaction of O(+) forms nascent parent ions in the excited à state, and internal conversion to the ground state only results in ejection of single D atom. Selected isotopomers of methanol were employed to identify reaction products, demonstrating that deuterium atom loss from nascent parent ions occurs by C-D bond cleavage. Comparison of the kinetic energy distributions for charge transfer to form CD3OD(+) and CD2OD(+) by D atom loss with the known dynamics for hy...Continue Reading

References

Aug 1, 1952·Proceedings of the National Academy of Sciences of the United States of America·H M RosenstockH Eyring
Aug 2, 2006·Physical Chemistry Chemical Physics : PCCP·J MikoschR Wester
Jul 7, 2007·The Journal of Chemical Physics·Li LiuJames M Farrar
Jan 12, 2008·Science·J MikoschR Wester
Jan 21, 2005·Physical Chemistry Chemical Physics : PCCP·Vincenzo AquilantiToshio Kasai
Jun 7, 2012·The Journal of Chemical Physics·Linsen Pei, James M Farrar
Apr 6, 2013·The Journal of Chemical Physics·Linsen Pei, James M Farrar

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Citations

Nov 15, 2017·Chemical Society Reviews·Eduardo CarrascosaRoland Wester
Oct 19, 2017·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Andrea CernutoDaniela Ascenzi
Sep 28, 2017·The Journal of Physical Chemistry. a·Justin P WiensNicholas S Shuman

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