Nonradiative decay pathways of electronic states of group IV tetrafluoro and tetrachloro molecular ions studied with synchrotron radiation

Article abstract of DOI:10.1063/1.458810

The nonradiative decay channels of the valence electronic states of the gas-phase tetrahedral ions CF4⁺, SiF4⁺, CCl4⁺, SiCl4⁺, and GeCl4⁺ have been studied in the range 35-100 nm by a novel form of photoionization mass spectrometry.Tunable vacuum UV radiation from a synchrotron source ionizes the parent neutral molecule, and electrons and ions are detected by the photoelectron-photoion coincidence technique.The experiment is repeated continuously as a function of photon energy, and a three-dimensional histogram of photon energy versus ion time of flight versus coincidence count rate is produced.By taking cuts through this histogram, photoionization curves for the different fragment ions can be extracted.The appearance energies of the fragment ions (e.g., CF2⁺ from CF4, CCl⁺ from CCl4) occur at the adiabatic ionization potential of an electronic state of the parent ion, and not at the thermodynamic appearance energy of that ion.Attempts to measure the kinetic-energy releases in the fragmentation pathways have only been partially successful.The results are complementary to those of recent experiments to probe the radiative decay of these electronic states of MX4⁺ , where the <*>T₂ and <*>A₁ third and fourth excited electronic states can show radiative decay to a surprising degree.The decay dynamics of the <*> and <*> states of MX4⁺ are reviewed.In general, the fluorides show different behavior to the analogous chlorides, and the carbon species behaves differently to the corresponding silicon or germanium species.

Full text of DOI:10.1063/1.458810

Nonradiative decay pathways of electronic states of group IV tetrafluoro and
tetrachloro molecular ions studied with synchrotron radiation
J. C. Creasey, I. R. Lambert, R. P. Tuckett, K. Codling, L. J. Frasinski, P. A. Hatherly, M. Stankiewicz, and D.
M. P. Holland
Citation: The Journal of Chemical Physics 93, 3295 (1990); doi: 10.1063/1.458810
View online: http://dx.doi.org/10.1063/1.458810
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/93/5?ver=pdfcov
Published by the AIP Publishing
Articles you may be interested in
Theoretical study of radiative and non-radiative decay processes in pyrazine derivatives
J. Chem. Phys. 135, 014304 (2011); 10.1063/1.3606579
Molecular electronics studies by synchrotron radiation
AIP Conf. Proc. 1092, 1 (2009); 10.1063/1.3086225
Radiative and nonradiative decay of electronically excited NCO
J. Chem. Phys. 104, 8279 (1996); 10.1063/1.471580
Decay pathways of excited electronic states of Group IV tetrafluoro and tetrachloro molecular ions studied
with synchrotron radiation
J. Chem. Phys. 89, 2683 (1988); 10.1063/1.455019
Electronic emission spectroscopy of Group IV tetrachloro molecular ions
J. Chem. Phys. 89, 2675 (1988); 10.1063/1.455018
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
131.193.242.64 On: Thu, 04 Dec 2014 02:01:33

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
131.193.242.64 On: Thu, 04 Dec 2014 02:01:33

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
131.193.242.64 On: Thu, 04 Dec 2014 02:01:33

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
131.193.242.64 On: Thu, 04 Dec 2014 02:01:33

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
131.193.242.64 On: Thu, 04 Dec 2014 02:01:33

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
131.193.242.64 On: Thu, 04 Dec 2014 02:01:33

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
131.193.242.64 On: Thu, 04 Dec 2014 02:01:33

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
131.193.242.64 On: Thu, 04 Dec 2014 02:01:33

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
131.193.242.64 On: Thu, 04 Dec 2014 02:01:33

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
131.193.242.64 On: Thu, 04 Dec 2014 02:01:33

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
131.193.242.64 On: Thu, 04 Dec 2014 02:01:33

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
131.193.242.64 On: Thu, 04 Dec 2014 02:01:33

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
131.193.242.64 On: Thu, 04 Dec 2014 02:01:33