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Title: A comparison of neutral and charged species of one- and two-dimensional models of graphene nanoribbons using multireference theory

This study examines the dependence of the polyradical character of charged quasi-linear n-acenes and two-dimensional periacenes used as models for graphene nanoribbons in comparison to the corresponding neutral compounds. For this purpose, high-level ab initio calculations have been performed using the multireference averaged quadratic coupled cluster theory. Vertical ionization energies and electron affinities have been computed. Systematic tests show that the dependence on chain length of these quantities can be obtained from a consideration of the π system only and that remaining contributions coming from the σ orbitals or extended basis sets remain fairly constant. Using best estimate values, the experimental values for the ionization energy of the acene series can be reproduced within 0.1 eV and the experimental electron affinities within 0.4 V. The analysis of the natural orbital occupations and related unpaired electron densities shows that the ionic species exhibit a significant decrease in polyradical character and thus an increased chemical stability as compared to the neutral state.
Authors:
 [1] ;  [1] ;  [2]
  1. Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409-1061 (United States)
  2. (Austria)
Publication Date:
OSTI Identifier:
22416070
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 5; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AFFINITY; COMPARATIVE EVALUATIONS; ELECTRON DENSITY; EV RANGE; GRAPHENE; LENGTH; NANOSTRUCTURES; PHASE STABILITY; TWO-DIMENSIONAL SYSTEMS