Oliveira, AM, Lehman, JH orcid.org/0000-0001-6610-6519 and Lineberger, WC (2018) Photoelectron Spectroscopy of the Aminomethoxide Anion, H₂C(NH₂)O⁻. Journal of Physical Chemistry A, 122 (22). pp. 4954-4962. ISSN 1089-5639
Abstract
We report the photoelectron spectrum of the aminomethoxide anion (H₂C(NH₂)O⁻). The electron affinity (EA) of the aminomethoxy radical is determined to be 1.944(1) eV. Transitions to the ground (X̃ ²A″) and first excited (Ã ²A′) electronic states of aminomethoxy are observed, with the term energy measured to be T₀(Ã ← X̃) = 0.085(1) eV. A long vibrational progression is observed for the transition to the ground X̃ ²A″ electronic state of aminomethoxy, primarily consisting of OCN bending and HNH wagging vibrations, leading to the assignment of these two fundamental vibrational frequencies of H₂C(NH₂)O· X̃ ²A″. The gas-phase acidity of aminomethanol is calculated at the G4 level of theory to be ΔacidH0Ko = 374.0 kcal mol⁻¹, which, when combined with the experimental EA of aminomethoxy in a thermochemical cycle, provides a determination of the O–H bond dissociation energy, D₀(H₂C(NH₂)O–H) as 106(2) kcal mol⁻¹. Comparisons of the EAs and T₀(Ã ← X̃) for the aminomethoxy, methoxy, ethoxy, and hydroxymethoxy radicals provides insight into how the substituent group affects the electronic structure of singly substituted alkoxy radicals.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2018 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry A after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpca.8b02921. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Physical Chemistry (Leeds) |
Funding Information: | Funder Grant number EU - European Union 743642 |
Depositing User: | Symplectic Publications |
Date Deposited: | 14 May 2018 14:26 |
Last Modified: | 10 May 2019 00:43 |
Status: | Published |
Publisher: | American Chemical Society |
Identification Number: | 10.1021/acs.jpca.8b02921 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:130739 |