Multistate effects in calculations of the electronic coupling element for electron transfer using the generalized Mulliken-Hush method

Journal of Physical Chemistry A

Volumn 106, Issue 15, 2002, Pages 3930-3940

  Rust, Michael ^a,b   Lappe, Jason ^a   Cave, Robert J ^a  

^a HARVEY MUDD COLLEGE   (United States)

^b HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

DIMETHYLAMINOBENZONITRILE; ELECTRON TRANSFER; ELECTRONIC COUPLING ELEMENT; MULLIKEN-HUSH METHOD;

APPROXIMATION THEORY; CHARGE TRANSFER; ELECTRON ENERGY LEVELS; ELECTRONIC STRUCTURE; ETHYLENE; MATHEMATICAL MODELS; NUMERICAL ANALYSIS; ORGANIC COMPOUNDS; POSITIVE IONS; SUBSTITUTION REACTIONS;

ELECTRON TRANSPORT PROPERTIES;

EID: 0037129508     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp0142886     Document Type: Article

References (59)

1. Marcus, R. A.; Sutin, N. Biochim. Biophys. Acta 1985, 265, 811.
2. Newton, M. D.; Cave, R. J. In Molecular Electronics; Ratner, M. A., Jortner, J., Eds.; IUPAC: London, 1996); p 73.
3. Marcus, R. A. J. Chem. Phys. 1965, 43, 679 and references cited therein.
4. Hush, N. S. Trans. Faraday Soc. 1961, 57, 557.
5. Levich, V. G.; Dogonadze, R. R. Collect. Czech. Chem. Commun. 1961, 26, 193.
6. Perng, B. C.; Newton, M. D.; Raineri, F. O.; Friedman, H. L. J. Chem. Phys. 1996, 104, 7153, 7177.
7. Matyushov, D. V. Chem. Phys. 1993, 174, 199.
8. Liu, Y. P.; Newton, M. D. J. Phys. Chem. 1995, 99, 12382.
9. Kurnikov, I. V.; Zusman, L. D.; Kurnikova, M. G.; Farid, R. S.; Beratan, D. N. J. Am. Chem. Soc. 1997, 119, 5690.
10. Mikkelsen, K. V.; Cesar, A.; Agren, H.; Jensen, H. A. J. Chem. Phys. 1995, 103, 9010.
11. McConnell, H. M. J. Chem. Phys. 1961, 35, 508.
12. Halpern, J.; Orgel, L. E.; Discuss. Faraday Soc. 1960, 29, 32.
13. Skourtis, S. S.; Beratan, D. N. Adv. Chem. Phys. 1999, 106, 377.
14. Onuchic, J. N.; Beratan, D. N.; Winkler, J. R.; Gray, H. B. Annu. Rev., Biophys. Biomol. Struct. 1992, 21, 349.
15. Liang, C.; Newton, M. D. J. Phys. Chem. 1992, 96, 2855
16. Liang, C.; Newton, M. D. J. Phys. Chem. 1993, 97, 3199.
17. Curtis, L. A.; Naleway, C. A.; Miller, J. R. J. Phys. Chem. 1995, 99, 1182
18. Jordan, K. D.; Nachtigallova, D. Paddon-Row, M. N. In Modern Electronic Structure Theory and Applications in Organic Chemistry; Davidson, E. R., Ed.; World Scientific: River Edge, NJ, 1997; p 257.
19. Newton, M. D. Chem. Rev. 1991, 91, 767.
20. Newton, M. D. Int. J. Quantum Chem.: Quantum Chem. Symp. 1980, 14, 363 and references cited therein.
21. Stuchebrukhov, A. A. Chem. Phys. Lett. 1994, 225, 55.
22. Stuchebrukhov, A. A. J. Chem. Phys. 1998, 108, 8499.
23. Larsson, S. J. Phys. Chem. 1984, 88, 1321.
24. Prezhdo, O. V.; Kindt, J. T.; Tully, J. C. J. Chem. Phys. 1999, 111, 7818.
25. Cave, R. J.; Baxter, D. V.; Goddard, W. A., III; Baldeschwieler, J. D. J. Chem. Phys. 1987, 87, 926.
26. Cave, R. J.; Newton, M. D. Chem. Phys. Lett. 1996, 249, 15.
27. Mulliken, R. S. J. Am. Chem. Soc. 1952, 811.
28. Hush, N. S. Prog. Inorg. Chem. 1967, 8, 391.
29. Hush, N. S. Electrochim. Acta 1968, 13, 1005.
30. Reimers, J. R.; Hush, N. S. J. Phys. Chem. 1991, 95, 9773.
31. Creutz, C.; Newton, M. D.; Sutin, N. J. Photochem. Photobiol. A 1994, 82, 47.
32. Murrell, J. N. J. Am. Chem. Soc. 1959, 81, 5037.
33. Mulliken, R. S.; Person, W. B. In Molecular Complexes: A Lecture and Reprint Volume; Wiley: New York, 1969.
34. Bixon, M.; Jortner, J.; Verhoeven, J. W. J. Am. Chem. Soc. 1994, 116, 7349.
35. Gould, I. R.; Young, R. H.; Mueller, L. J.; Albrecht, A. C.; Farid, S. J. Am. Chem. Soc. 1994, 116, 8188, 8176.
36. Herbich, J.; Kapturkiewicz, A. J. Am. Chem. Soc. 1998, 120, 1014.
37. Czerwieniec, R.; Herbich, J.; Kapturkiewicz, A.; Nowacki, J. Chem. Phys. Lett. 2000, 325, 589.
38. Herbich, J.; Kapturkiewicz, A.; Nowacki, J.; Golinski, J.; Dabrowski, Z. Phys. Chem. Chem. Phys. 2001, 3, 2438.
39. Löwdin, P. O. J. Math. Phys. 1962, 3, 969.
40. The adiabatic energy matrix is diagonal and the GS and CT states are assumed to be composed largely of adiabatic states 1 and 2 in case 3. In cases 1 and 2, similar reasoning suggests that variation in the ratio of coefficients should alter the estimated coupling element.
41. 33), leading to eq 11. This approximation is made to obtain a more compact expression for the diagnostic. It could be relaxed but generally need not be. Except where the mixing between the GS and CT state is large, or the CT distance is quite short, this approximation will be valid.
42. Jones, G., II. Private communication.
43. Jones, G., II; Farahat, M. S.; Greenfield, S. R.; Gosztola, D. J.; Wasielewski, M. R. Chem. Phys. Lett. 1994, 229, 40.
44. Allen, H. C.; Plyler, E. K. J. Am. Chem. Soc. 1958, 80, 2673.
45. 2v symmetry, with C-H bonds of 1.081 Å, N-H bonds of 1.081 Å, a C-N bond of 1.282 Å, an HCH angle of 121.2°, and an HNH angle of 117.0°.
46. Ditchfield, R.; Hehre, W. J.; Pople, J. A. J. Chem. Phys. 1971, 56, 724.
47. Head-Gordon, M. J.; Pople, J. A.; Frisch, M. J. Chem. Phys. Lett. 1988, 153, 503.
48. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A., Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B. G.; Chen, W.; Wong, M. W.; Andres, J. L.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98 (Revision A.7); Gaussian, Inc.: Pittsburgh, PA, 1998.
49. Clark, T.; Chandreshakhar, J.; Spitznagel, G. W.; Schleyer, P. v. R.; J. Comput. Chem. 1983, 4, 294.
50. Foresman, J. B.; Head-Gordon, M.; Pople, J. A.; Frisch. M. J. J. Phys. Chem. 1992, 96, 135.
51. From the point of view of application of the GMH approach this is the appropriate dipole moment to use, since it is the field-free mixing of the diabetic states that one transforms away in the diagonalization of the dipole moment matrix.
52. Modest differences arise due to our (a) use of the GMH rather than MH result for the dipole difference, (b) allowance for differences in dipole moments between the GS and LE state, and (c) use of energetic quantities obtained from a single nuclear configuration.
53. Zerner, M. C. ZINDO, 3.7 ed.; Molecular Simulations Inc.: San Diego, CA, 1991.
54. Lippert, E.; Lüder, W.; Boos, H. In Advanced molecular spectroscopy; Mangini, A., Ed.; Pergamon Press: New York, 1962; Vol. 1, p 443.
55. Menunucci, B.; Toniolo, A.; Tomasi, J. J. Am. Chem. Soc. 2000, 122, 10621.
56. Serrano-Andrés, L.; Merchán, M.; Roos, B. O.; Lindh, R. J. Am. Chem. Soc. 1995, 117, 3189.
57. Dewar, M. J. S.; Zoebish, E. G.; Healy, E. F. J. Am. Chem. Soc. 1985, 107, 3902.
58. Alaishuski, L.; Cave, R. J. Unpublished results.
59. D in each case predicts a 30% change (indicative of a large correction to the numerator in eq 19, while the second ε term and the δ term in eq 19 are indicative of significant changes in diagonal dipole moments upon addition of a third state); nevertheless, the 2-state and 3-state coupling elements are quite similar. However, this equivalence arises from a cancellation of the contributions from the ε and δ terms in the actual 3-state results, which only partially cancel in the first-order treatment (eq 19). Thus, while there is significant state mixing, the net result is a small change in the coupling.