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A spectroscopic investigation of the ionisation and dissociation decay dynamics of Rydberg states of NO

Minns, RS; Lazenby, DTC; Hall, FHJ; Jones, NJA; Patel, R; Fielding, HH; (2014) A spectroscopic investigation of the ionisation and dissociation decay dynamics of Rydberg states of NO. MOLECULAR PHYSICS , 112 (13) 1808 - 1815. 10.1080/00268976.2013.865809. Green open access

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Abstract

Double-resonance spectroscopy has been employed to characterise the autoionising and predissociating Rydberg states of NO converging to the υ+ = 0 and υ+ = 1 levels of the X1Σ+ ground state of NO+. Below the lowest ionisation limit, we monitor the formation of the N(2D) predissociation product and observe a spectrum dominated by the p(N+ = 0) series, with smaller contributions from the p(2) and f(2) series. Many of the lineshapes can be fit to a simple Fano line profile. Upon vibrational excitation, a competing autoionisation channel is opened and we monitor the products of both the dissociation and ionisation channels. The υ+ = 1 predissociation spectrum appears much more complex than the predissociation spectrum, with significant contributions from the p(0), f(2), p(2), s(1) and d(1) series. In contrast, the υ+ = 1 ionisation spectrum is dominated by the p(0) and f(2) Rydberg series, with much weaker contributions from s(1), d(1) and p(2) series. The lineshapes in the υ+ = 1 predissociation and autoionisation spectra are perturbed and cannot be fit to simple Fano line profiles. In some extreme cases, these perturbations result in the complete disappearance of peaks from either the autoionisation or predissociation spectrum.

Type: Article
Title: A spectroscopic investigation of the ionisation and dissociation decay dynamics of Rydberg states of NO
Open access status: An open access version is available from UCL Discovery
DOI: 10.1080/00268976.2013.865809
Publisher version: http://dx.doi.org/10.1080/00268976.2013.865809
Language: English
Additional information: © 2014 The Author(s). Published by Taylor & Francis. This is an Open Access article distributed under the terms of the Creative Commons Attribution License http://creativecommons.org/licenses/by/3.0/, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. The moral rights of the named author(s) have been asserted.
Keywords: Rydberg states, spectroscopy, autoionisation, predissociation
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/1452186
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