Hückel Molecular Orbital Quantities of {X,Y}-Cyclacene Graphs Under Next-Nearest-Neighbour Approximations in Analytical Forms.

Hückel molecular orbital (HMO) quantities, viz., electron densities, charge densities, bond orders, free valences, total π-electron energies and highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO–LUMO) or band gaps of {X,Y}-cyclacene graphs under next-nearest-neighbour (nnn...

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Publicado en:Zeitschrift für Naturforschung Section A: A Journal of Physical Sciences Vol. 74; no. 6; pp. 469 - 489
Autores principales: Ghosh, Tapanendu, Mondal, Swapnadeep, Mondal, Sukanya, Mandal, Bholanath
Formato: Artículo
Publicado: De Gruyter Jun2019
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Acceso en línea:Ver este registro en EBSCOhost
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        137129428
        10.1515/zna-2018-0488
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        atl: Hückel Molecular Orbital Quantities of {X,Y}-Cyclacene Graphs Under Next-Nearest-Neighbour Approximations in Analytical Forms.
      aug:
        au:
          Ghosh, Tapanendu
          Mondal, Swapnadeep
          Mondal, Sukanya
          Mandal, Bholanath
        affil: Department of Chemistry, The University of Burdwan, Burdwan 713104, India
      su:
        Hückel molecular orbitals
        Electron density
        Molecular orbitals
        Strain energy
        Density of states
      sug:
        subj:
          Hückel molecular orbitals
          Electron density
          Molecular orbitals
          Strain energy
          Density of states
      keyword:
        Cyclacene Graphs
        Cyclic Dimer and HOMO–LUMO Gap
        Electron Density-Bond Order-Free Valence
        Next-Nearest-Neighbour Approximations
        Total π-Electron Energy
      ab: Hückel molecular orbital (HMO) quantities, viz., electron densities, charge densities, bond orders, free valences, total π-electron energies and highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO–LUMO) or band gaps of {X,Y}-cyclacene graphs under next-nearest-neighbour (nnn) approximations are expressed in analytical forms within a certain range of nnn approximation parameter (m). The critical values of m for {X,Y}-cyclacenes with varying X (=C, N, B) and Y (=C, N, B) are calculated. For {X,X}-cyclacenes with a π-electron on each atom, all HMO quantities except total π-electron energies for a given value of m are found to be independent of X. The cyclic dimer (CD) is constructed in obtaining the eigenvalues corresponding to the singular points of the density of states (DOS) of such {X,Y}-cyclacene. Although the HOMO–LUMO gap of the CD differs from that of the cyclacene with a large number of repeating units (i.e. n ⟶ ∞) but becomes the same for m = 0. The analytical expressions can be used for facile computer programming in obtaining the HMO quantities. Such nnn interaction approximations actually release, to some extent, the strain that results in due to the geometrical structures of such cyclacenes, which is evident from the plots of strain energy per segment vs. contribution of such interactions on the total π-electron energy, where the slopes decrease with an increase in m. The vertical absorption energy difference for singlet-triplet states bears excellent linear correlation with the HOMO–LUMO gaps for a certain m value (m = 0.3) in the case of an even n, but for an odd n, such energy difference remains invariant.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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