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Wigner Near-Threshold Effects in the Photoelectron Angular Distribution of NO2-

Laws, Benjamin; Cavanagh, Steven; Lewis, Brenton; Gibson, Stephen

Description

High-resolution velocity map imaged photoelectron spectra of the nitrite anion NO2- are measured over a range of photodetachment wavelengths between 355 and 550 nm, resolving the vibrational and rotational structure of the NO2(X̃2A1) + e- ← NO2-(X̃1A1) + hν transition. A full rotational band model is constructed to define the spectroscopic constants of both the neutral and the lesser studied anion ground states. The corresponding photoelectron angular distributions are characterized by a large...[Show more]

dc.contributor.authorLaws, Benjamin
dc.contributor.authorCavanagh, Steven
dc.contributor.authorLewis, Brenton
dc.contributor.authorGibson, Stephen
dc.date.accessioned2020-11-06T03:20:12Z
dc.identifier.citationJ. Phys. Chem. A 2019, 123, 10418−10425
dc.identifier.issn1089-5639
dc.identifier.urihttp://hdl.handle.net/1885/214097
dc.description.abstractHigh-resolution velocity map imaged photoelectron spectra of the nitrite anion NO2- are measured over a range of photodetachment wavelengths between 355 and 550 nm, resolving the vibrational and rotational structure of the NO2(X̃2A1) + e- ← NO2-(X̃1A1) + hν transition. A full rotational band model is constructed to define the spectroscopic constants of both the neutral and the lesser studied anion ground states. The corresponding photoelectron angular distributions are characterized by a large positive anisotropy parameter, with β ≈ 1.5 gradually increasing to β ≈ 1.7 upon approaching the threshold. However, at very low kinetic energies, within 0.1 eV of the threshold, β dramatically drops to 0. This behavior is a consequence of the Wigner near-threshold selectivity of the electron partial-wave cross sections, whereby an atomic p-like orbital character adjacent to the threshold is favored. The full kinetic energy dependence of β is reproduced by a new mixed spd orbital model, yielding a NO2-(X̃1A1) molecular-orbital decomposition of 2% p, 44% s, and 54% d character.
dc.description.sponsorshipThis research was supported by the Australian Research Council Discovery Project Grant DP160102585.
dc.format.mimetypeapplication/pdf
dc.language.isoen_AU
dc.publisherAmerican Chemical Society
dc.rights© 2019 American Chemical Society
dc.sourceJournal of Physical Chemistry A
dc.titleWigner Near-Threshold Effects in the Photoelectron Angular Distribution of NO2-
dc.typeJournal article
local.description.notesImported from ARIES
local.identifier.citationvolume123
dc.date.issued2019-11-11
local.identifier.absfor030606 - Structural Chemistry and Spectroscopy
local.identifier.ariespublicationu5786633xPUB1255
local.publisher.urlhttps://pubs.acs.org/
local.type.statusPublished Version
local.contributor.affiliationLaws, Benjamin, College of Science, ANU
local.contributor.affiliationCavanagh, Steven, College of Science, ANU
local.contributor.affiliationLewis, Brenton, College of Science, ANU
local.contributor.affiliationGibson, Stephen, College of Science, ANU
local.description.embargo2037-12-31
dc.relationhttp://purl.org/au-research/grants/arc/DP160102585
local.bibliographicCitation.issue48
local.bibliographicCitation.startpage10418
local.bibliographicCitation.lastpage10425
local.identifier.doi10.1021/acs.jpca.9b09073
local.identifier.absseo970103 - Expanding Knowledge in the Chemical Sciences
dc.date.updated2022-05-29T08:18:05Z
local.identifier.scopusID2-s2.0-85075460435
local.identifier.thomsonIDWOS:000501623400008
CollectionsANU Research Publications

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