Funct. Mater. 2020; 27 4: 800-810.
doi:https://doi.org/10.15407/fm27.04.800
Singlet open-shell conjugated networks generated by singular graphs: Use of Huckel-like models
SSI Institute of Single Crystals, National Academy of Sciences of Ukraine, 60 Nauky Ave., 61001 Kharkiv, Ukraine
Abstract:
We show how the conventional tight-binding (TB), i. e., Huckel method can be consistently extended to open-shell singlet ground states of polyradical alternant systems that correspond to singular graphs. This leads us to the open-shell TB (OS-TB) model which is presented in detail and compared here with more complicated π-electron approximations. In particular, the earlier introduced quasi-correlated TB (QCTB) method and its extension (EQC) are involved into assessing the accuracy of OS-TB. It is shown that commonly used bond-order matrices, as well as electron-unpairing densities are described well by OS-TB, whereas π-electron Green functions generally are not. At the same time, we demonstrate that the related models, QCTB and EQC, provide reasonable estimates of molecular conductance (at the Fermi energy) in polyradical conjugated networks. The obtained results may be used for a design of active molecular elements in nanoelectronics.
Keywords:
polyradicals, electron unpairing, singular molecular graphs, long-range effects, spin correlators, molecular conductance.
References:
| 1. A.D.Guclu, P.Potasz, M.Korkusinski, P.Hawrylak, Graphene Quantum Dots, Springer, Berlin (2014). https://doi.org/10.1007/978-3-662-44611-9 |
||||
| 2. R.Saito, G.Dresselhaus, M.S.Dresselhaus, Physical Properties of Carbon Nanotubes, Imperial College Press, London (1998). https://doi.org/10.1142/p080 |
||||
| 3. M.Damnjanovi'c, I.Milo'sevi'c, Line Groups in Physics-Theory and Applications to Nanotubes and Polymers, Springer, Berlin Heidelberg (2010). | ||||
| 4. M.Nakano, B.Champagne, J. Phys. Chem. Lett., 6, 3236 (2015) https://doi.org/10.1021/acs.jpclett.5b00956 |
||||
| M.Nakano, Chem. Rec., 17, 27 (2017). https://doi.org/10.1002/tcr.201600094 |
||||
| 5. C.L.Wang, H.L.Dong, W.P.Hu et al., Chem. Rev., 112, 2208 (2012). https://doi.org/10.1021/cr100380z |
||||
| 6. Z.Bullard, E.C.Girao, J.R.Owens et al., Sci. Rep., 5, 7634 (2015). https://doi.org/10.1038/srep07634 |
||||
| 7. J.R.Dias, G.G.Cash, J. Chem. Inf. Comput. Sci., 41, 129 (2001) https://doi.org/10.1021/ci000064t |
||||
| J.R.Dias, Open Org. Chem. J., 5, 112 (2011). https://doi.org/10.2174/1874364101105010112 |
||||
| 8. G.L.Collatz. U.Sinogowitz, Abh. Math. Semin. Univ. Hamb., 21, 63 (1957). https://doi.org/10.1007/BF02941924 |
||||
| 9. I.Sciriha, Electron. J. Algebra, 16, 451 {2007). https://doi.org/10.13001/1081-3810.1215 |
||||
| 10. A.V.Luzanov, Funct. Mater., 21, 437 (2014). https://doi.org/10.15407/fm21.04.437 |
||||
| 11. A.V.Luzanov, in: Practical Aspects of Computational Chemistry IV, ed. by J.Leszczynski, M.K.Shukla, Springer, New York (2016), p.151. | ||||
| 12. A.V.Luzanov, F.Plasser, A.Das, H.Lischka, J. Chem. Phys., 146, 064106 (2017). https://doi.org/10.1063/1.4975196 |
||||
| 13. G.G.Hall, Proc. R. Soc. A, 229, 251(1955). https://doi.org/10.1098/rspa.1955.0085 |
||||
| 14. C.A.Coulson, G.S.Rushbrooke, Proc. Cambridge Phil. Soc., 36, 193 (1940). https://doi.org/10.1017/S0305004100017163 |
||||
| 15. S.G.Davison, A.T.Amos, J. Chem. Phys., 43, 2223 (1965). https://doi.org/10.1063/1.1697114 |
||||
| 16. A.Graovac, O.E.Polansky, N.Trinajstic, N.Tyutyulkov, Z. Naturforsch., 30a, 1696 (1975). https://doi.org/10.1515/zna-1975-1230 |
||||
| 17. D.Doehnert, J.Koutecky, J. Am. Chem. Soc., 102, 1789 (1980). https://doi.org/10.1021/ja00526a005 |
||||
| 18. M.Head-Gordon, Chem. Phys. Lett., 372, 508 (2003). https://doi.org/10.1016/S0009-2614(03)00422-6 |
||||
| 19. A.V.Luzanov, in: Nanophotonics, Nanooptics, Nanobiotechnology, and Their Applications (NANO 2018) (Springer Proceedings in Physics); ed.by O.Fesenko, L.Yatsenko, Springer, Cham., v.222 (2019), p.341. | ||||
| 20. H.C.Longuet-Higgins, J. Chem. Phys., 18, 265 (1950). https://doi.org/10.1063/1.1747618 |
||||
| 21. A.V.Luzanov, Funct. Mater., 27,147, (2020). | ||||
| 22. M.M.Mestechkin, G.T.Klimko, V.A.Kuz'mitskii, Teor. Eksp. Khim., 20, 641 (1984). | ||||
| 23. G.T.Klimko, M.M.Mestechkin, B.N.Plakhutin, G.M.Zhidomirov, Int. J. Quantum Chem., 37, 35 (1990). https://doi.org/10.1002/qua.560370104 |
||||
| 24. C.C.J.Roothaan, Rev. Mod. Phys., 32, 179 (1960). https://doi.org/10.1103/RevModPhys.32.179 |
||||
| 25. K.K.Stavrev, M.C.Zerner, Int. J. Quantum. Chem., 65, 877 (1997). https://doi.org/10.1002/(SICI)1097-461X(1997)65:5<877::AID-QUA51>3.0.CO;2-T |
||||
| 26. W.G.Penney, Proc. Roy. Soc. A, 158, 306 (1937). https://doi.org/10.1098/rspa.1937.0022 |
||||
| 27. K.B.Wiberg, Tetrahedron, 24, 1083 (1968). https://doi.org/10.1016/0040-4020(68)88057-3 |
||||
| 28. A.V.Luzanov, O.V.Prezhdo, I. J. Quantum Chem. Phys., 102, 582 (2005). https://doi.org/10.1002/qua.20438 |
||||
| 29. A.V.Luzanov, I. J. Quantum Chem. Phys., 112, 2915 (2012). https://doi.org/10.1002/qua.24101 |
||||
| 30. M.Rosenberg, Mol. Phys., 30, 1037 (1975). https://doi.org/10.1080/00268977500102581 |
||||
| 31. J.A.Pople, D.P.Santry, Mol. Phys., 9, 301 (1965). https://doi.org/10.1080/00268976500100431 |
||||
| 32. H.E.Zimmerman, Quantum Mechanics for Organic Chemists, Academic Press, New York (1975). | ||||
| 33. A.V.Luzanov, Y.F.Pedash, S.Mohamad, Theor. Experim. Chem., 26, 513 (1990). https://doi.org/10.1007/BF00531900 |
||||
| 34. A.V.Luzanov, Kharkov Univ. Bull., Chem. Ser., 31(54), 6 (2018). | ||||
| 35. A.V.Luzanov, Funct. Mater., 26, 152 (2019). https://doi.org/10.15407/fm26.01.152 |
||||
| 36. J.D.Roberts, A.Streitwieser, C.M.Regan, J. Am. Chem. Soc., 74, 4579 (1952). https://doi.org/10.1021/ja01138a038 |
||||
| 37. M.M.Mestechkin, G.E.Whyman, Mol. Phys., 69, 775 (1990). https://doi.org/10.1080/00268979000100571 |
||||
| 38. A.A.Ovchinnikov, Theor. Chem. Acta, 47, 297 (1978) https://doi.org/10.1007/BF00549259 |
||||
| E.H.Lieb, Phys. Rev. Lett., 62, 1201 (1989). https://doi.org/10.1103/PhysRevLett.62.1201 |
||||
| 39. J.C.Cuevas, E.Scheer, Molecular Electronics: An Introduction to Theory and Experiment, World Scientific, Singapore (2010). https://doi.org/10.1142/7434 |
||||
| 40. Y.Tsuji, E.Estrada, R.Movassagh, R.Hoffmann, Chem. Rev., 118, 4887 (2018). https://doi.org/10.1021/acs.chemrev.7b00733 |
||||
| 41. T.Stuyver, T.Zeng, Y.Tsuji et al., Nano Letters, 18, 7298 (2018). https://doi.org/10.1021/acs.nanolett.8b03503 |
||||
| 42. M.H.Garner, W.Bro-Jorgensen, P.D.Pedersen, G.C.Solomon, J. Phys. Chem. C, 122, 26777 (2018). https://doi.org/10.1021/acs.jpcc.8b05661 |
||||
| 43. N.Algethami, H.Sadeghi, S.Sangtarash, C.J.Lambert, Nano Letters, 18, 4482 (2018). https://doi.org/10.1021/acs.nanolett.8b01621 |
||||
| 44. K.G.L.Pedersen, M.Strange, M.Leijnse et al., Phys. Rev. B, 90, 125413 (2014). https://doi.org/10.1103/PhysRevB.90.125413 |
||||
.