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Title: Negative ion photoelectron spectroscopy of P 2N 3 : Electron affinity and electronic structures of P 2N 3 ˙

The recent successful synthesis of P 2N 3 , a planar all-inorganic aromatic molecule, represents a breakthrough in inorganic chemistry, because, like its isolobal counterparts C 5H 5– and cyclo-P 5 , P 2N 3 has potential to serve as a new ligand for transition metals and a building block in solid-state molecular architectures. In light of its importance, we report here a negative ion photoelectron spectroscopy (NIPES) and ab initio study of P 2N 3 , to investigate the electronic structures of P 2N 3 and its neutral P 2N 3• radical. The adiabatic detachment energy of P 2N 3 (electron affinity of P 2N 3•) was determined to be 3.765 ± 0.010 eV, indicating high stability for the P 2N 3 anion. Ab initio electronic structure calculations reveal five low-lying electronic states in the neutral P 2N 3• radical. Calculation of the Franck-Condon factors (FCFs) for each anion-to-neutral electronic transition and comparison of the resulting simulated NIPE spectrum with the vibrational structure in the observed spectrum allows the first four excited states of P 2N 3• to be determined to lie 6.2, 6.7, 11.5, and 22.8 kcal/mol -1 above the ground state of themore » radical, which is found to be a 6π-electron, 2A 1, σ state.« less
Authors:
 [1] ;  [2] ;  [3] ;  [4] ;  [3] ;  [4] ;  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Cornell Univ., Ithaca, NY (United States)
  3. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  4. Univ. of North Texas, Denton, TX (United States)
Publication Date:
Report Number(s):
PNNL-SA-114862
Journal ID: ISSN 2041-6520; CSHCBM; 48584; KC0301050
Grant/Contract Number:
AC05-76RL01830
Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 7; Journal Issue: 7; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Research Org:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Environmental Molecular Sciences Laboratory
OSTI Identifier:
1324892

Hou, Gao -Lei, Chen, Bo, Transue, Wesley J., Hrovat, David A., Cummins, Christopher C., Borden, Weston Thatcher, and Wang, Xue -Bin. Negative ion photoelectron spectroscopy of P2N3–: Electron affinity and electronic structures of P2N3 ˙. United States: N. p., Web. doi:10.1039/C5SC04667J.
Hou, Gao -Lei, Chen, Bo, Transue, Wesley J., Hrovat, David A., Cummins, Christopher C., Borden, Weston Thatcher, & Wang, Xue -Bin. Negative ion photoelectron spectroscopy of P2N3–: Electron affinity and electronic structures of P2N3 ˙. United States. doi:10.1039/C5SC04667J.
Hou, Gao -Lei, Chen, Bo, Transue, Wesley J., Hrovat, David A., Cummins, Christopher C., Borden, Weston Thatcher, and Wang, Xue -Bin. 2016. "Negative ion photoelectron spectroscopy of P2N3–: Electron affinity and electronic structures of P2N3 ˙". United States. doi:10.1039/C5SC04667J. https://www.osti.gov/servlets/purl/1324892.
@article{osti_1324892,
title = {Negative ion photoelectron spectroscopy of P2N3–: Electron affinity and electronic structures of P2N3 ˙},
author = {Hou, Gao -Lei and Chen, Bo and Transue, Wesley J. and Hrovat, David A. and Cummins, Christopher C. and Borden, Weston Thatcher and Wang, Xue -Bin},
abstractNote = {The recent successful synthesis of P2N3–, a planar all-inorganic aromatic molecule, represents a breakthrough in inorganic chemistry, because, like its isolobal counterparts C5H5– and cyclo-P5–, P2N3– has potential to serve as a new ligand for transition metals and a building block in solid-state molecular architectures. In light of its importance, we report here a negative ion photoelectron spectroscopy (NIPES) and ab initio study of P2N3–, to investigate the electronic structures of P2N3– and its neutral P2N3• radical. The adiabatic detachment energy of P2N3– (electron affinity of P2N3•) was determined to be 3.765 ± 0.010 eV, indicating high stability for the P2N3– anion. Ab initio electronic structure calculations reveal five low-lying electronic states in the neutral P2N3• radical. Calculation of the Franck-Condon factors (FCFs) for each anion-to-neutral electronic transition and comparison of the resulting simulated NIPE spectrum with the vibrational structure in the observed spectrum allows the first four excited states of P2N3• to be determined to lie 6.2, 6.7, 11.5, and 22.8 kcal/mol-1 above the ground state of the radical, which is found to be a 6π-electron, 2A1, σ state.},
doi = {10.1039/C5SC04667J},
journal = {Chemical Science},
number = 7,
volume = 7,
place = {United States},
year = {2016},
month = {4}
}

Works referenced in this record:

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993
  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913