Negative Ion Photoelectron Spectroscopy Confirms the Prediction of a Singlet Ground State for the 1,8-Naphthoquinone Diradical

Yang, Zheng; Hrovat, David A.; Hou, Gao -Lei; Borden, Weston Thatcher; Wang, Xue -Bin

doi:10.1021/acs.jpca.8b11063

Title: Negative Ion Photoelectron Spectroscopy Confirms the Prediction of a Singlet Ground State for the 1,8-Naphthoquinone Diradical

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Abstract

Negative ion photoelectron (NIPE) spectra, with 193, 266, 300, and 355 nm photons, of the radical anion of 1,8-naphthoquinone (1,8-NQ^•-) have been obtained at 20K. The electron affinity of 1,8-NQ is determined from the first resolved peak in the NIPE spectrum to be 2.98 ± 0.04 eV. Franck-Condon factors (FCFs), calculated from the CASPT2/aug-cc-pVDZ optimized geometries, normal modes, and vibrational frequencies successfully simulate the intensity and frequencies of the spectral features that are associated with the lowest two electronic states. Here, the NIPE spectra of 1,8-NQ^•- and the peak assignments, based on the computed FCFs, confirm the theoretical predictions that ¹A₁ is the ground state of 1,8- NQ and that ³B₂ is the first excited state. The spectra provide an experimental value of ΔE_ST = -1.5 kcal/mol, which is within about 1 kcal/mol of the (12/12)CASPT2/aug-cc-pVTZ calculated value of ΔE_ST = -2.6 kcal/mol.

Authors:

^[1]; Hrovat, David A. ^[2];

^[1]; Borden, Weston Thatcher ^[2];

^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Univ. of North Texas, Denton, TX (United States)

Publication Date:: Thu Mar 14 00:00:00 EDT 2019

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1530598

Report Number(s):: PNNL-SA-139614
Journal ID: ISSN 1089-5639

Grant/Contract Number:: AC05-76RL01830

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

Additional Journal Information:: Journal Volume: 123; Journal Issue: 14; Journal ID: ISSN 1089-5639

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Yang, Zheng, Hrovat, David A., Hou, Gao -Lei, Borden, Weston Thatcher, and Wang, Xue -Bin. Negative Ion Photoelectron Spectroscopy Confirms the Prediction of a Singlet Ground State for the 1,8-Naphthoquinone Diradical.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.jpca.8b11063.

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                    Yang, Zheng, Hrovat, David A., Hou, Gao -Lei, Borden, Weston Thatcher, & Wang, Xue -Bin. Negative Ion Photoelectron Spectroscopy Confirms the Prediction of a Singlet Ground State for the 1,8-Naphthoquinone Diradical.  United States.  https://doi.org/10.1021/acs.jpca.8b11063

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                    Yang, Zheng, Hrovat, David A., Hou, Gao -Lei, Borden, Weston Thatcher, and Wang, Xue -Bin. Thu .  
"Negative Ion Photoelectron Spectroscopy Confirms the Prediction of a Singlet Ground State for the 1,8-Naphthoquinone Diradical".  United States.  https://doi.org/10.1021/acs.jpca.8b11063.  https://www.osti.gov/servlets/purl/1530598.

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@article{osti_1530598,

  title        = {Negative Ion Photoelectron Spectroscopy Confirms the Prediction of a Singlet Ground State for the 1,8-Naphthoquinone Diradical},

  author       = {Yang, Zheng and Hrovat, David A. and Hou, Gao -Lei and Borden, Weston Thatcher and Wang, Xue -Bin},

  abstractNote = {Negative ion photoelectron (NIPE) spectra, with 193, 266, 300, and 355 nm photons, of the radical anion of 1,8-naphthoquinone (1,8-NQ•-) have been obtained at 20K. The electron affinity of 1,8-NQ is determined from the first resolved peak in the NIPE spectrum to be 2.98 ± 0.04 eV. Franck-Condon factors (FCFs), calculated from the CASPT2/aug-cc-pVDZ optimized geometries, normal modes, and vibrational frequencies successfully simulate the intensity and frequencies of the spectral features that are associated with the lowest two electronic states. Here, the NIPE spectra of 1,8-NQ•- and the peak assignments, based on the computed FCFs, confirm the theoretical predictions that 1A1 is the ground state of 1,8- NQ and that 3B2 is the first excited state. The spectra provide an experimental value of ΔEST = -1.5 kcal/mol, which is within about 1 kcal/mol of the (12/12)CASPT2/aug-cc-pVTZ calculated value of ΔEST = -2.6 kcal/mol.},

  doi          = {10.1021/acs.jpca.8b11063},

  journal      = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},

  number       = 14,

  volume       = 123,

  place        = {United States},

  year         = {Thu Mar 14 00:00:00 EDT 2019},

  month        = {Thu Mar 14 00:00:00 EDT 2019}

}

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