Electron affinities, well depths, and vibrational spectroscopy of cis - And trans -HOCO

Christopher J. Johnson; Michael E. Harding; Berwyck L.J. Poad; John F. Stanton; Robert E. Continetti

doi:10.1021/ja207724f

Electron affinities, well depths, and vibrational spectroscopy of cis - And trans -HOCO

Christopher J. Johnson
, Michael E. Harding
, Berwyck L.J. Poad
, John F. Stanton
, Robert E. Continetti

Chemistry

University of Texas at Austin
University of California at San Diego

Research output: Contribution to journal › Article › peer-review

45 Scopus citations

Abstract

We report vibrationally resolved photoelectron spectra of internally cold HOCO^- and DOCO^- anions at wavelengths near and well above the detachment threshold. These spectra are dominated by a strong Franck-Condon progression of three low-energy modes of the cis isomer, the first gas-phase measurement of these vibrations. Using highly resolved, near-threshold spectra we are able to reassign the electron affinities (EAs) of cis- and trans-HOCO to 1.51 ± 0.01 and 1.37 ± 0.01 eV, respectively. Using these EAs, well depths with respect to OH + CO are determined to be 1.07 ± 0.02 eV for trans-HOCO and 0.99 ± 0.02 eV for cis-HOCO. High-level ab initio calculations show excellent agreement with all experimental results. These values will be of direct use in thermochemical calculations and will help to aid in the identification of the HOCO radical in complex reactions.

Original language	English
Pages (from-to)	19606-19609
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	133
Issue number	49
DOIs	https://doi.org/10.1021/ja207724f
State	Published - Dec 14 2011

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title = "Electron affinities, well depths, and vibrational spectroscopy of cis - And trans -HOCO",

abstract = "We report vibrationally resolved photoelectron spectra of internally cold HOCO- and DOCO- anions at wavelengths near and well above the detachment threshold. These spectra are dominated by a strong Franck-Condon progression of three low-energy modes of the cis isomer, the first gas-phase measurement of these vibrations. Using highly resolved, near-threshold spectra we are able to reassign the electron affinities (EAs) of cis- and trans-HOCO to 1.51 ± 0.01 and 1.37 ± 0.01 eV, respectively. Using these EAs, well depths with respect to OH + CO are determined to be 1.07 ± 0.02 eV for trans-HOCO and 0.99 ± 0.02 eV for cis-HOCO. High-level ab initio calculations show excellent agreement with all experimental results. These values will be of direct use in thermochemical calculations and will help to aid in the identification of the HOCO radical in complex reactions.",

author = "Johnson, \{Christopher J.\} and Harding, \{Michael E.\} and Poad, \{Berwyck L.J.\} and Stanton, \{John F.\} and Continetti, \{Robert E.\}",

year = "2011",

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day = "14",

doi = "10.1021/ja207724f",

language = "English",

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journal = "Journal of the American Chemical Society",

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TY - JOUR

T1 - Electron affinities, well depths, and vibrational spectroscopy of cis - And trans -HOCO

AU - Johnson, Christopher J.

AU - Harding, Michael E.

AU - Poad, Berwyck L.J.

AU - Stanton, John F.

AU - Continetti, Robert E.

PY - 2011/12/14

Y1 - 2011/12/14

N2 - We report vibrationally resolved photoelectron spectra of internally cold HOCO- and DOCO- anions at wavelengths near and well above the detachment threshold. These spectra are dominated by a strong Franck-Condon progression of three low-energy modes of the cis isomer, the first gas-phase measurement of these vibrations. Using highly resolved, near-threshold spectra we are able to reassign the electron affinities (EAs) of cis- and trans-HOCO to 1.51 ± 0.01 and 1.37 ± 0.01 eV, respectively. Using these EAs, well depths with respect to OH + CO are determined to be 1.07 ± 0.02 eV for trans-HOCO and 0.99 ± 0.02 eV for cis-HOCO. High-level ab initio calculations show excellent agreement with all experimental results. These values will be of direct use in thermochemical calculations and will help to aid in the identification of the HOCO radical in complex reactions.

AB - We report vibrationally resolved photoelectron spectra of internally cold HOCO- and DOCO- anions at wavelengths near and well above the detachment threshold. These spectra are dominated by a strong Franck-Condon progression of three low-energy modes of the cis isomer, the first gas-phase measurement of these vibrations. Using highly resolved, near-threshold spectra we are able to reassign the electron affinities (EAs) of cis- and trans-HOCO to 1.51 ± 0.01 and 1.37 ± 0.01 eV, respectively. Using these EAs, well depths with respect to OH + CO are determined to be 1.07 ± 0.02 eV for trans-HOCO and 0.99 ± 0.02 eV for cis-HOCO. High-level ab initio calculations show excellent agreement with all experimental results. These values will be of direct use in thermochemical calculations and will help to aid in the identification of the HOCO radical in complex reactions.

UR - https://www.scopus.com/pages/publications/83055179157

U2 - 10.1021/ja207724f

DO - 10.1021/ja207724f

M3 - Article

AN - SCOPUS:83055179157

SN - 0002-7863

VL - 133

SP - 19606

EP - 19609

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 49

ER -

Electron affinities, well depths, and vibrational spectroscopy of cis - And trans -HOCO

Abstract

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