Triplet-singlet gap in structurally flexible organic diradicals
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| 008 | 210128e20150201xx s 000 0 eng | ||
| 024 | 7 | 0 | |a 10.1007/s00214-015-1619-5 |2 doi |
| 035 | |a (NATIONALLICENCE)springer-10.1007/s00214-015-1619-5 | ||
| 245 | 0 | 0 | |a Triplet-singlet gap in structurally flexible organic diradicals |h [Elektronische Daten] |c [Daniel Reta Mañeru, Ibério de Moreira, Francesc Illas] |
| 520 | 3 | |a A key factor in the search of high-spin ground state purely organic molecules concerns the effect of the inherent non-rigid structures on the magnetic and optical properties. This structural feature has not been properly addressed in previous theoretical works. Here, based on the experimentally characterized high-spin ground state of dendritic and star-branched polyradicals, we study four alternant hydrocarbon biradicals that intend to model these effects and, at the same time, provide a first step toward understanding more extended experimental structures. A series of density functional theory (DFT) and of wave function-based methods have been used to explore the richness of structural minima in the corresponding potential energy surfaces and to discuss its effect on the triplet-singlet gap of the proposed model systems. For a given model, the DFT-based B3LYP, M06-2X and MN-12SX methods provide a consistent description. Likewise, a multiconfigurational quasi-degenerate perturbation theory approach with the minimal π space as CASSCF reference is found to provide unbiased results. Despite the conformational richness found for these systems, they all can be described by a reduced set of values referred to only two structural parameters, being those the dihedral angles between the phenyl rings. For a given model, there is no significant change in the triplet-singlet gap depending on the chosen local minima. | |
| 540 | |a Springer-Verlag Berlin Heidelberg, 2015 | ||
| 690 | 7 | |a Diradicals |2 nationallicence | |
| 690 | 7 | |a Triplet-singlet gap |2 nationallicence | |
| 690 | 7 | |a CASSCF |2 nationallicence | |
| 690 | 7 | |a MRQDPT |2 nationallicence | |
| 690 | 7 | |a DFT |2 nationallicence | |
| 700 | 1 | |a Reta Mañeru |D Daniel |u Departament de Química Física & Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, C/ Martí i Franquès 1, 08028, Barcelona, Spain |4 aut | |
| 700 | 1 | |a Moreira |D Ibério de |u Departament de Química Física & Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, C/ Martí i Franquès 1, 08028, Barcelona, Spain |4 aut | |
| 700 | 1 | |a Illas |D Francesc |u Departament de Química Física & Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, C/ Martí i Franquès 1, 08028, Barcelona, Spain |4 aut | |
| 773 | 0 | |t Theoretical Chemistry Accounts |d Springer Berlin Heidelberg |g 134/2(2015-02-01), 1-10 |x 1432-881X |q 134:2<1 |1 2015 |2 134 |o 214 | |
| 856 | 4 | 0 | |u https://doi.org/10.1007/s00214-015-1619-5 |q text/html |z Onlinezugriff via DOI |
| 898 | |a BK010053 |b XK010053 |c XK010000 | ||
| 900 | 7 | |a Metadata rights reserved |b Springer special CC-BY-NC licence |2 nationallicence | |
| 908 | |D 1 |a research-article |2 jats | ||
| 949 | |B NATIONALLICENCE |F NATIONALLICENCE |b NL-springer | ||
| 950 | |B NATIONALLICENCE |P 856 |E 40 |u https://doi.org/10.1007/s00214-015-1619-5 |q text/html |z Onlinezugriff via DOI | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Reta Mañeru |D Daniel |u Departament de Química Física & Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, C/ Martí i Franquès 1, 08028, Barcelona, Spain |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Moreira |D Ibério de |u Departament de Química Física & Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, C/ Martí i Franquès 1, 08028, Barcelona, Spain |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Illas |D Francesc |u Departament de Química Física & Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, C/ Martí i Franquès 1, 08028, Barcelona, Spain |4 aut | ||
| 950 | |B NATIONALLICENCE |P 773 |E 0- |t Theoretical Chemistry Accounts |d Springer Berlin Heidelberg |g 134/2(2015-02-01), 1-10 |x 1432-881X |q 134:2<1 |1 2015 |2 134 |o 214 | ||