Résumé
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.
| langue originale | Anglais |
|---|---|
| Pages (de - à) | 431-436 |
| Nombre de pages | 6 |
| journal | Theoretical Chemistry Accounts |
| Volume | 105 |
| Numéro de publication | 6 |
| Les DOIs | |
| état | Publié - 1 mai 2001 |
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Möbius strip versus linear and cyclic polyacenes : A Hückel and semiempirical investigation. / Guillaume, Maxime; Champagne, Benoît; Perpète, Eric A.; André, Jean-Marie.
Dans: Theoretical Chemistry Accounts, Vol 105, Numéro 6, 01.05.2001, p. 431-436.Résultats de recherche: Contribution à un journal/une revue › Article
TY - JOUR
T1 - Möbius strip versus linear and cyclic polyacenes
T2 - A Hückel and semiempirical investigation
AU - Guillaume, Maxime
AU - Champagne, Benoît
AU - Perpète, Eric A.
AU - André, Jean-Marie
PY - 2001/5/1
Y1 - 2001/5/1
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.
KW - Austin Model 1 Energy gap
KW - Möbius strip
KW - Polyacenes
UR - http://www.scopus.com/inward/record.url?scp=0035587434&partnerID=8YFLogxK
U2 - 10.1007/s002140000245
DO - 10.1007/s002140000245
M3 - Article
AN - SCOPUS:0035587434
VL - 105
SP - 431
EP - 436
JO - Theoretical Chemistry Accounts: Theory, Computation, and Modeling
JF - Theoretical Chemistry Accounts: Theory, Computation, and Modeling
SN - 1432-881X
IS - 6
ER -