Oliveira, AM, Lehman, JH orcid.org/0000-0001-6610-6519, McCoy, AB et al. (1 more author) (2016) Photoelectron spectroscopy of the hydroxymethoxide anion, H 2 C(OH)O −. The Journal of Chemical Physics, 145 (12). 124317. ISSN 0021-9606
Abstract
We report the negative ion photoelectron spectroscopy of the hydroxymethoxide anion, H2C(OH)O − . The photoelectron spectra show that 3.49 eV photodetachment produces two distinct electronic states of the neutral hydroxymethoxy radical (H2C(OH)O · ). The H2C(OH)O · ground state (X˜ 2A) photoelectron spectrum exhibits a vibrational progression consisting primarily of the OCO symmetric and asymmetric stretches, the OCO bend, as well as combination bands involving these modes with other, lower frequency modes. A high-resolution photoelectron spectrum aids in the assignment of several vibrational frequencies of the neutral H2C(OH)O · radical, including an experimental determination of the H2C(OH)O · 2ν12 overtone of the H–OCO torsional vibration as 220(10) cm−1 . The electron affinity of H2C(OH)O · is determined to be 2.220(2) eV. The low-lying A˜ 2A excited state is also observed, with a spectrum that peaks ∼0.8 eV above the X˜ 2A state origin. The A˜ 2A state photoelectron spectrum is a broad, partially resolved band. Quantum chemical calculations and photoelectron simulations aid in the interpretation of the photoelectron spectra. In addition, the gas phase acidity of methanediol is calculated to be 366(2) kcal mol−1 , which results in an OH bond dissociation energy, D0(H2C(OH)O–H), of 104(2) kcal mol−1 , using the experimentally determined electron affinity of the hydroxymethoxy radical.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2016, the Author(s). This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. The following article appeared in Oliveira, AM, Lehman, JH , McCoy, AB et al. (1 more author) (2016) Photoelectron spectroscopy of the hydroxymethoxide anion, H 2 C(OH)O −. The Journal of Chemical Physics, 145 (12). 124317. ISSN 0021-9606 and may be found at https://doi.org/10.1063/1.4963225. |
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) |
Depositing User: | Symplectic Publications |
Date Deposited: | 07 Feb 2017 16:28 |
Last Modified: | 11 Apr 2017 00:53 |
Published Version: | https://doi.org/10.1063/1.4963225 |
Status: | Published |
Publisher: | AIP Publishing |
Identification Number: | 10.1063/1.4963225 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:111916 |