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Title: Negative ion photoelectron spectroscopy of P2N3: Electron affinity and electronic structures of P2N3 ˙

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.
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:
OSTI Identifier:
1324892
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