Optical properties and charge-transfer excitations in edge-functionalized all-graphene nanojunctions

Journal of Physical Chemistry Letters

Volumn 2, Issue 11, 2011, Pages 1315-1319

  Cocchi, Caterina ^a,b   Prezzi, Deborah ^a   Ruini, Alice ^a,b   Caldas, Marilia J ^c   Molinari, Elisa ^a,b  

^a CNR   (Italy)

^b UNIVERSITY OF MODENA AND REGGIO EMILIA   (Italy)

^c UNIVERSITY OF SÃO PAULO   (Brazil)

Author keywords

[No Author keywords available]

Indexed keywords

CHARGE-TRANSFER EXCITATIONS; LOW ENERGY REGIONS; LOW-ENERGY EXCITATIONS; MOLECULAR FUNCTIONALIZATION; NANOJUNCTIONS; OPTOELECTRONIC NANODEVICES; OSCILLATOR STRENGTHS; TUNABILITIES; UV-VIS SPECTRA;

CHARGE TRANSFER; ELECTRONIC PROPERTIES; FUNCTIONAL GROUPS; GRAPHENE; HYDROCARBONS; NANOSYSTEMS; POLYCYCLIC AROMATIC HYDROCARBONS;

OPTICAL PROPERTIES;

EID: 79958194499     PISSN: None     EISSN: 19487185     Source Type: Journal    
DOI: 10.1021/jz200472a     Document Type: Article

References (37)

1. Loh, K.; Bao, Q.; Ang, P.; Yang, J. The Chemistry of Graphene J. Mater. Chem. 2010, 20, 2277-2289
2. Tyutyulkov, N.; Madjarova, G.; Dietz, F.; Mullen, K. Is 2-D Graphite an Ultimate Large Hydrocarbon? 1. Energy Spectra of Giant Polycyclic Aromatic Hydrocarbons J. Phys. Chem. B 1998, 102, 10183-10189 (Pubitemid 128621226)
3. Watson, M. D.; Fechtenkötter, A.; Muellen, K. Big Is Beautiful - "Aromaticity" Revisited from the Viewpoint of Macromolecular and Supramolecular Benzene Chemistry Chem. Rev. 2001, 101, 1267-1300 (Pubitemid 35375209)
4. Wu, J.; Pisula, W.; Muellen, K. Graphenes as Potential Material for Electronics Chem. Rev. 2007, 107, 718-747 (Pubitemid 46504818)
5. Cai, J.; Ruffieux, P.; Jaafar, R.; Bieri, M.; Braun, T.; Blankenburg, S.; Muoth, M.; Seitsonen, A. P.; Saleh, M.; Feng, X.; Muellen, K. Atomically Precise Bottom-Up Fabrication of Graphene Nanoribbons Nature (London) 2010, 466, 470-473
6. Qian, H.; Negri, F.; Wang, C.; Wang, Z. Fully Conjugated Tri(perylene bisimides): An Approach to the Construction of n-Type Graphene Nanoribbons J. Am. Chem. Soc. 2008, 130, 17970-17976
7. Wang, X.; Li, X.; Zhang, L.; Yoon, Y.; Weber, P. K.; Wang, H.; Guo, J.; Dai, H. N-Doping of Graphene Through Electrothermal Reactions with Ammonia Science 2009, 324, 768-771
8. Li, Y.; Gao, J.; Di Motta, S.; Negri, F.; Wang, Z. Tri-N-annulated Hexarylene: An Approach to Well-Defined Graphene Nanoribbons with Large Dipoles J. Am. Chem. Soc. 2010, 132, 4208-4213
9. Naghavi, S. S.; Gruhn, T.; Alijani, V.; Fecher, G. H.; Felser, C.; Medjanik, K.; Kutnyakhov, D.; Nepijko, S. A.; Schönhense, G.; Rieger, R. Theoretical Study of New Acceptor and Donor Molecules Based on Polycyclic Aromatic Hydrocarbons J. Mol. Spectrosc. 2011, 265, 95-101
10. Prezzi, D.; Varsano, D.; Ruini, A.; Marini, A.; Molinari, E. Optical Properties of Graphene Nanoribbons: The Role of Many-Body Effects Phys. Rev. B 2008, 77, 041404/1-041404/4
11. Prezzi, D.; Varsano, D.; Ruini, A.; Marini, A.; Molinari, E. Optical Properties of One-Dimensional Graphene Polymers: The Case of Polyphenanthrene Phys. Status Solidi B 2007, 244, 4124-4128
12. Prezzi, D.; Varsano, D.; Ruini, A.; Molinari, E. Quantum-Dot States and Optical Excitations in Edge-Modulated Graphene Nanoribbons. Cond-Mat 2011, arXiv1104.3519 (1-4).
13. Yang, L.; Cohen, M.; Louie, S. Excitonic Effects in the Optical Spectra of Graphene Nanoribbons Nano Lett. 2007, 7, 3112-3115 (Pubitemid 350139072)
14. Zhu, X.; Su, H. Excitons of Edge and Surface Functionalized Graphene Nanoribbons J. Phys. Chem. C 2010, 114, 17257-17262
15. Cocchi, C.; Ruini, A.; Prezzi, D.; Caldas, M. J.; Molinari, E. Designing All-Graphene Nanojunctions by Covalent Functionalization J. Phys. Chem. C 2011, 115, 2969-2973
16. Ridley, J.; Zerner, M. An Intermediate Neglect of Differential Overlap Technique for Spectroscopy: Pyrrole and the Azines Theor. Chem. Acta 1973, 32, 111-134
17. Caldas, M. J.; Pettenati, E.; Goldoni, G.; Molinari, E. Tailoring of Light Emission Properties of Functionalized Oligothiophenes Appl. Phys. Lett. 2001, 79, 2505-2507 (Pubitemid 33599616)
18. Wang, Z.; Tomovic?, Z.; Kastler, M.; Pretsch, R.; Negri, F.; Enkelmann, V.; Muellen, K. Graphitic Molecules with Partial "Zig/Zag" Periphery J. Am. Chem. Soc. 2004, 126, 7794-7795 (Pubitemid 38812767)
19. Dewar, M. J. S.; Zoebish, E. G.; Healy, E. F.; Stewart, J. J. P. A New General Purpose Quantum Mechanical Molecular Model J. Am. Chem. Soc. 1985, 107, 3902-3909
20. AM1 and ZINDO/S calculations were performed using VAMP package included in Accelrys Materials Studio software, version 5.0; http://accelrys.com/ products/materials-studio. We have chosen CI energy windows that include at least 4 eV below the HOMO and 3 eV above the LUMO in order to ensure convergence.
21. Son, Y.-W.; Cohen, M. L.; Louie, S. G. Energy Gaps in Graphene Nanoribbons Phys. Rev. Lett. 2006, 97, 216803/1-216803/4
22. Barone, V.; Hod, O.; Scuseria, G. E. Electronic Structure and Stability of Semiconducting Graphene Nanoribbons Nano Lett. 2006, 6, 2748-2754 (Pubitemid 46129565)
23. Hod, O.; Barone, V.; Scuseria, G. E. Half-Metallic Graphene Nanodots: A Comprehensive First-Principles Theoretical Study Phys. Rev. B 2008, 77, 035411/1-035411/6
24. Zhang, Q.; Prins, P.; Jones, S. C.; Barlow, S.; Kondo, T.; An, Z.; Siebbeles, L. D. A.; Marder, S. R. A Fluorine-Substituted Hexakisdecyloxy- hexa- peri -hexabenzocoronene Org. Lett. 2005, 7, 5019-5022
25. Kikuzawa, Y.; Mori, T.; Takeuchi, H. Synthesis of 2,5,8,11,14,17- Hexafluoro-hexa- peri-hexabenzocoronene for n-Type Organic Field-Effect Transistors Org. Lett. 2007, 9, 4817-4820
26. 2 functionalization and hydrogenated afterwards. No significant changes have been observed in the UV-vis spectra nor in the composition of the excitation, as a consequence of distortions. The detailed results of this test are reported in the Supporting Information.
27. An analogous behavior is observed also in conjugated copolymers, characterized by an alternation of donor and acceptor units, which induces a localization of frontier orbitals and consequently of hole and electron densities as well. See, for example: Jespersen, K. G.; Beenken, W. J. D.; Zaushitsyn, Y.; Yartsev, A.; Andersson, M.; Pullerits, T.; Sundstrom, V. The Electronic States of Polyfluorene Copolymers with Alternating Donor-Acceptor Units J. Chem. Phys. 2004, 121, 12613-12617 For a recent review on these systems, see: Chen, Y.-J.; Yang, S.-H.; Hsu, C.-S. Synthesis of Conjugated Polymers for Organic Solar Cell Applications Chem. Rev. 2009, 109, 5868-5923 (Pubitemid 41041619)
28. Baierle, R. J.; Caldas, J.; Molinari, E.; Ossicini, S. Optical Emission from Small Si Particles Solid State Commun. 1997, 102, 545-549 (Pubitemid 127418593)
29. Ruini, A.; Caldas, M. J.; Bussi, G.; Molinari, E. Solid State Effects on Exciton States and Optical Properties of PPV Phys. Rev. Lett. 2002, 88, 206403/1-206403/4
30. Jensen, F. Introduction to Computational Chemistry, 2nd ed.; Wiley: New York, 2007.
31. Seitsonen, A. P.; Saitta, A. M.; Wassmann, T.; Lazzeri, M.; Mauri, F. Structure and Stability of Graphene Nanoribbons in Oxygen, Carbon Dioxide, Water, and Ammonia Phys. Rev. B 2010, 82, 115425/1-115425/6
32. Cervantes-Sodi, F.; Csányi, G.; Piscanec, S.; Ferrari, A. C. Edge-Functionalized and Substitutionally Doped Graphene Nanoribbons: Electronic and Spin Properties Phys. Rev. B 2008, 77, 165427/1-165427/13
33. Ren, H.; Li, Q.; Su, H.; Shi, Q. W.; Chen, J.; Yang, J. Edge Effects on the Electronic Structures of Chemically Modified Armchair Graphene Nanoribbons. Cond-Mat 2007, arXiv0711.1700v1 (1-5).
34. Kan, E.-j.; Li, Z.; Yang, J.; Hou, J. G. Half-Metallicity in Edge-Modified Zigzag Graphene Nanoribbons J. Am. Chem. Soc. 2008, 130, 4224-4225 (Pubitemid 351466405)
35. Zheng, H.; Duley, W. First-Principles Study of Edge Chemical Modifications in Graphene Nanodots Phys. Rev. B 2008, 78, 045421/1-045421/5
36. Gunlycke, D.; Mintmire, J. W.; White, C. T. Robust Ballistic Transport in Narrow Armchair-Edge Graphene Nanoribbons with Chemical Edge Disorder J. Phys. Chem. Lett. 2010, 1, 1082-1085
37. 2//F functionalization, where the first excitation is optically active and presents charge-transfer character for all of the considered families. See the Supporting Information for a more detailed discussion.