Möbius strip versus linear and cyclic polyacenes: A Hückel and semiempirical investigation

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Abstract

The electronic structure of finite and infinite linear, cyclic and Möbius strip polyacenes has been investigated by adopting Hückel and semiempirical schemes. Using the Hückel approach, it turns out that the Möbius belting process modifies the highest occupied molecular orbital (HOMO) - lowest unoccupied molecular orbital (LUMO) gap in such a way its evolution with chain length is similar to the linear polyacenes rather than their cyclic analogs. These results are corroborated at the Austin model 1 (AM 1) level, where the geometry relaxation effects are taken into account. The optimized AM 1 structures show that the Möbius defect is localized and extends over a third of the ring. With respect to the Hückel approach, accounting for geometry distortion at the AM 1 levels results in an increase in the HOMO-LUMO gap of the Möbius strip relative to the linear and cyclic finite-size structures. On the other hand, when including electron-hole correlation at the configuration interaction singles Zerner's intermediate neglect of differential overlap level the behavior with system size of the first excitation energy of cyclic and Möbius polyacenes differs from their linear analogs and leads to smaller singlet excitation energies.

Original languageEnglish
Pages (from-to)431-436
Number of pages6
JournalTheoretical Chemistry Accounts
Volume105
Issue number6
DOIs
Publication statusPublished - 1 May 2001

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Aromatic polymers
Molecular orbitals
strip
molecular orbitals
Excitation energy
analogs
Geometry
geometry
Chain length
configuration interaction
excitation
Electronic structure
electronic structure
Defects
energy
Electrons
rings
defects
austin

Keywords

  • Austin Model 1 Energy gap
  • Möbius strip
  • Polyacenes

Cite this

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title = "M{\"o}bius strip versus linear and cyclic polyacenes: A H{\"u}ckel and semiempirical investigation",
abstract = "The electronic structure of finite and infinite linear, cyclic and M{\"o}bius strip polyacenes has been investigated by adopting H{\"u}ckel and semiempirical schemes. Using the H{\"u}ckel approach, it turns out that the M{\"o}bius belting process modifies the highest occupied molecular orbital (HOMO) - lowest unoccupied molecular orbital (LUMO) gap in such a way its evolution with chain length is similar to the linear polyacenes rather than their cyclic analogs. These results are corroborated at the Austin model 1 (AM 1) level, where the geometry relaxation effects are taken into account. The optimized AM 1 structures show that the M{\"o}bius defect is localized and extends over a third of the ring. With respect to the H{\"u}ckel approach, accounting for geometry distortion at the AM 1 levels results in an increase in the HOMO-LUMO gap of the M{\"o}bius strip relative to the linear and cyclic finite-size structures. On the other hand, when including electron-hole correlation at the configuration interaction singles Zerner's intermediate neglect of differential overlap level the behavior with system size of the first excitation energy of cyclic and M{\"o}bius polyacenes differs from their linear analogs and leads to smaller singlet excitation energies.",
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AU - André, Jean-Marie

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N2 - The electronic structure of finite and infinite linear, cyclic and Möbius strip polyacenes has been investigated by adopting Hückel and semiempirical schemes. Using the Hückel approach, it turns out that the Möbius belting process modifies the highest occupied molecular orbital (HOMO) - lowest unoccupied molecular orbital (LUMO) gap in such a way its evolution with chain length is similar to the linear polyacenes rather than their cyclic analogs. These results are corroborated at the Austin model 1 (AM 1) level, where the geometry relaxation effects are taken into account. The optimized AM 1 structures show that the Möbius defect is localized and extends over a third of the ring. With respect to the Hückel approach, accounting for geometry distortion at the AM 1 levels results in an increase in the HOMO-LUMO gap of the Möbius strip relative to the linear and cyclic finite-size structures. On the other hand, when including electron-hole correlation at the configuration interaction singles Zerner's intermediate neglect of differential overlap level the behavior with system size of the first excitation energy of cyclic and Möbius polyacenes differs from their linear analogs and leads to smaller singlet excitation energies.

AB - The electronic structure of finite and infinite linear, cyclic and Möbius strip polyacenes has been investigated by adopting Hückel and semiempirical schemes. Using the Hückel approach, it turns out that the Möbius belting process modifies the highest occupied molecular orbital (HOMO) - lowest unoccupied molecular orbital (LUMO) gap in such a way its evolution with chain length is similar to the linear polyacenes rather than their cyclic analogs. These results are corroborated at the Austin model 1 (AM 1) level, where the geometry relaxation effects are taken into account. The optimized AM 1 structures show that the Möbius defect is localized and extends over a third of the ring. With respect to the Hückel approach, accounting for geometry distortion at the AM 1 levels results in an increase in the HOMO-LUMO gap of the Möbius strip relative to the linear and cyclic finite-size structures. On the other hand, when including electron-hole correlation at the configuration interaction singles Zerner's intermediate neglect of differential overlap level the behavior with system size of the first excitation energy of cyclic and Möbius polyacenes differs from their linear analogs and leads to smaller singlet excitation energies.

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