Calculations of electron transport through simple π-and σ-type radicals

Journal of Physical Chemistry C

Volumn 114, Issue 41, 2010, Pages 17874-17879

  Smeu, Manuel ^a   Dilabio, Gino A ^b,c  

^a MCGILL UNIVERSITY   (Canada)

^b NATIONAL RESEARCH COUNCIL CANADA   (Canada)

^c UNIVERSITY OF ALBERTA   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

AU ELECTRODES; BENZENE RING; ELECTRON TRANSPORT; ENERGY LEVEL; FIRST-PRINCIPLES; NONEQUILIBRIUM GREEN'S FUNCTION TECHNIQUE; ORGANIC RADICALS; SINGLY OCCUPIED MOLECULAR ORBITALS; SPIN FILTERS; TRANSPORT CALCULATION; UNPAIRED ELECTRONS;

BENZENE; CHEMICAL BONDS; DENSITY FUNCTIONAL THEORY; ELECTRODES; ELECTRON TRANSITIONS; ELECTRON TRANSPORT PROPERTIES; GREEN'S FUNCTION; MOLECULAR ELECTRONICS; MOLECULAR ORBITALS; MOLECULES; TRANSPORT PROPERTIES;

ELECTRON AFFINITY;

EID: 77958000454     PISSN: 19327447     EISSN: 19327455     Source Type: Journal    
DOI: 10.1021/jp105589y     Document Type: Article

References (50)

1. Carroll, R. L.; Gorman, C. B. Angew. Chem., Int. Ed. 2002, 41, 4378-4400
2. Lindsay, S. M.; Ratner, M. A. Adv. Mater. 2007, 19, 23-31
3. García-Suárez, V. M.; Lambert, C. J. Phys. Rev. B 2008, 78, 235412-1-235412-6
4. Maslyuk, V. V.; Bagrets, A.; Meded, V.; Arnold, A.; Evers, F.; Brandbyge, M.; Bredow, T.; Mertig, I. Phys. Rev. Lett. 2006, 97, 097201-1-097201-4
5. Koleini, M.; Paulsson, M.; Brandbyge, M. Phys. Rev. Lett. 2007, 98, 197202-1-197202-4
6. Mallajosyula, S. S.; Parida, P.; Pati, S. K. J. Mater. Chem. 2009, 19, 1761-1766
7. Wang, L.; Cai, Z.; Wang, J.; Lu, J.; Luo, G.; Lai, L.; Zhou, J.; Qin, R.; Gao, Z.; Yu, D.; Li, G.; Mei, W. N.; Sanvito, S. Nano Lett. 2008, 8, 3640-3644
8. Shen, X.; Yi, Z.; Shen, Z.; Zhao, X.; Wu, J.; Hou, S.; Sanvito, S. Nanotechnology 2009, 20, 385401-1-385401-9
9. Zhou, L.; Yang, S.-W.; Ng, M.-F.; Sullivan, M. B.; Tan, V. B. C.; Shen, L. J. Am. Chem. Soc. 2008, 130, 4023-4027
10. Wu, J.-C.; Wang, X.-F.; Zhou, L.; Da, H.-X.; Lim, K. H.; Yang, S.-W.; Li, Z.-Y. J. Phys. Chem. C 2009, 113, 7913-7916
11. Xu, K.; Huang, J.; Lei, S.; Su, H.; Boey, F. Y. C.; Li, Q.; Yang, J. J. Chem. Phys. 2009, 131, 104704-1-104704-6
12. Blase, X.; Margine, E. R. Appl. Phys. Lett. 2009, 94, 173103-1-173103-3
13. Tagami, K.; Tsukada, M. J. Phys. Chem. B 2004, 108, 6441-6444
14. Tao, N. J. Nat. Nanotechnol. 2006, 1, 173-181
15. The spin-filter performance of a system containing a europium- cyclooctatetraene sandwich structure has also been modeled (11)
16. Studer, A.; Schulte, T. Chem. Rec. 2005, 5, 27-35
17. Foti, M. C.; Daquino, C.; Mackie, I. D.; DiLabio, G. A.; Ingold, K. U. J. Org. Chem. 2008, 73, 9270-9282
18. Recent theoretical work by Tagami and Tsukada on a large, polyphenoxyl radical suggests that radicals could be used in this respect (13)
19. Herrmann, C.; Solomon, G. C.; Ratner, M. A. J. Am. Chem. Soc. 2010, 132, 3682-3684
20. Venkataraman, L.; Park, Y. S.; Whalley, A. C.; Nuckolls, C.; Hybertsen, M. S.; Steigerwald, M. L. Nano Lett. 2007, 7, 502-506
21. Gold-thiol linkages have been used extensively in the past to bridge small gaps created in break-junction experiments. (22) However, Wu et al. demonstrated recently that gold-amine linkages allow for electron transport through molecules that are within an order of magnitude of that achieved with gold-sulfur linkages (23)
22. Lindsay, S. M.; Ratner, M. A. Adv. Mater. 2007, 19, 23-41
23. Wu, S.; González, M. T.; Huber, R.; Grunder, S.; Mayor, M.; Schönenberger, C.; Calame, M. Nat. Nanotechnol. 2008, 3, 569-574
24. Frisch, M. J.; et al. Gaussian 03, Revision B.03; Gaussian, Inc.: Wallingford, CT, 2004.
25. Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652
26. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785-789
27. Ross, R. B.; Powers, J. M.; Atashroo, T.; Ermler, W. C.; LaJohn, L. A.; Christiansen, P. A. J. Chem. Phys. 1990, 93, 6654-6670
28. In an actual two-probe system the molecule would relax its geometry according to the positions of the electrodes. In these calculations the goal was to maximize the MO overlap between the electrodes and the molecule and this was achieved by also optimizing the position of the electrodes relative to each other.
29. Taylor, J.; Guo, H.; Wang, J. Phys. Rev. B 2001, 63, 245407-1-24507-13
30. Waldron, D.; Haney, P.; Larade, B.; MacDonald, A.; Guo, H. Phys. Rev. Lett. 2006, 96, 166804-1-166804-4
31. Datta, S. Electronic Transport in Mesoscopic Systems; Cambridge University Press: New York, 1995.
32. Lopez Sancho, M. P.; Lopez Sancho, J. M.; Rubio, J. J. Phys. F 1984, 14, 1205-1215
33. Büttiker, M.; Imry, Y.; Landauer, R.; Pinhas, S. Phys. Rev. B 1985, 31, 6207-6215
34. Troullier, N.; Martins, J. L. Phys. Rev. B 1991, 43, 1993-2006
35. von Barth, U.; Hedin, L. J. Phys. C 1972, 5, 1629-1642
36. Gunnarsson, O.; Lundqvist, B. I. Phys. Rev. B 1976, 13, 4274-4298
37. Rajagopal, A. K. J. Phys. C 1978, 11, L943-L948
38. Toher, C.; Sanvito, S. Phys. Rev. Lett. 2007, 99 056801
39. Ke, S.-H.; Baranger, H. U.; Yang, W. J. Chem. Phys. 2007, 126, 201102
40. One or more scattering states can be attributed to any transmission peak, which can then be projected onto the MOs of the molecule to determine which ones contribute to transmission at a particular energy. Each transmission peak is assigned to the MO that contributes the largest amount to its scattering states. Details on scattering states can be found in ref 29.
41. There are some sharp peaks labeled "lead" which are indeed due to high density of states in the electrodes at those particular energies and do not correspond to transmission through a particular MO.
42. We use this nomenclature to emphasize the relationship between these MOs. The SOMO is an α MO and the SUMO is its β analogue.
43. F opens the possibility for transport mechanisms other than resonant tunneling, which includes inelastic tunneling and charge hopping. Although the Landauer approach we used neglects these, we believe that resonant tunneling dominates at low bias for our small molecular system and that the other transport mechanisms play a relatively minimal role. This is because the likelihood for inelastic tunneling is proportional to the bias window, and charge hopping is unlikely for such small molecules that are well coupled to the electrodes, as studied in this work.
44. 2 groups leads to an attenuation of this effect.
45. Brown, H. C.; Okamoto, Y. J. Am. Chem. Soc. 1958, 80, 4979-4987
46. Pratt, D. A.; DiLabio, G. A.; Mulder, P.; Ingold, K. U. Acc. Chem. Res. 2004, 37, 334-340
47. All values reported in this table were obtained with the methodology used for the transport calculations.
48. DiLabio, G. A.; Pratt, D. A.; LoFaro, A. D.; Wright, J. S. J. Phys. Chem. A 1999, 103, 1653-1661
49. Solomon, G. C.; Andrews, D. Q.; Van Duyne, R. P.; Ratner, M. A. ChemPhysChem. 2009, 10, 257-264
50. F differs between bulk leads and leads that are very thin and essentially one-dimensional.