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Beyond the Born-Oppenheimer approximation: high-resolution overtone spectroscopy of H2D+ and D2H+

Fárník, M.; Davis, S.; Kostin, M.A.; Polyansky, O.L.; Tennyson, J.; Nesbitt, D.J.; (2002) Beyond the Born-Oppenheimer approximation: high-resolution overtone spectroscopy of H2D+ and D2H+. The Journal of Chemical Physics , 116 (14) pp. 6146-6158. 10.1063/1.1458244. Green open access

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Transitions to overtone 2v2 and 2v3, and combination v2 + v3 vibrations in jet-cooled H2D+ and D2H+ molecular ions have been measured for the first time by high-resolution IR spectroscopy. The source of these ions is a pulsed slit jet supersonic discharge, which allows for efficient generation, rotational cooling, and high frequency (100 KHz) concentration modulation for detection via sensitive lock-in detection methods. Isotopic substitution and high-resolution overtone spectroscopy in this fundamental molecular ion permit a systematic, first principles investigation of Born–Oppenheimer "breakdown" effects due to large amplitude vibrational motion as well as provide rigorous tests of approximate theoretical methods beyond the Born–Oppenheimer level. The observed overtone transitions are in remarkably good agreement (<0.1 cm–1) with non-Born–Oppenheimer ab initio theoretical predictions, with small but systematic deviations for 2v2, 2v + 3v, and 2v3 excited states indicating directions for further improvement in such treatments. Spectroscopic assignment and analysis of the isotopomeric transitions reveals strong Coriolis mixing between near resonant 2v3 and 2v + 3v vibrations in D2H+. Population-independent line intensity ratios for transitions from common lower states indicate excellent overall agreement with theoretical predictions for D2H+, but with statistically significant discrepancies noted for H2D+. Finally, H2D+ versus D2H+ isotopomer populations are analyzed as a function of D2/H2 mixing ratio and can be well described by steady state kinetics in the slit discharge expansion.

Type: Article
Title: Beyond the Born-Oppenheimer approximation: high-resolution overtone spectroscopy of H2D+ and D2H+
Open access status: An open access version is available from UCL Discovery
DOI: 10.1063/1.1458244
Publisher version: http://link.aip.org/link/?jcp/116/6146
Language: English
Additional information: Copyright 2002 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in The Journal of Chemical Physics, 116 (14). pp. 6146-6158 and may be found at http://link.aip.org/link/?jcp/116/6146.
UCL classification: UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy
URI: https://discovery.ucl.ac.uk/id/eprint/1171
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