Application of time-resolved linear dichroism spectroscopy: Rapid relaxation of excited charge transfer complexes

Journal of Physical Chemistry A

Volumn 105, Issue 45, 2001, Pages 10404-10412

  Arnold, Bradley R ^a   Euler, Alex ^a   Poliakov, Pavel V ^a   Schill, Alexander W ^a  

^a UNIVERSITY OF MARYLAND BALTIMORE COUNTY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHARGE TRANSFER COMPLEXES;

BENZENE; CHEMICAL RELAXATION; COMPLEXATION; ELECTRON ENERGY LEVELS; ELECTRON TRANSITIONS; PHOTOCHEMICAL REACTIONS; SPECTROSCOPIC ANALYSIS;

CHARGE TRANSFER;

EID: 0035892205     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp011929o     Document Type: Article

References (59)

1. Magde, D. J. Chem. Phys. 1978, 68, 3717-3733.
2. Ansari, A.; Szabo, A. Biophys. J. 1993, 64, 838-851.
3. Szabo, A. J. Chem. Phys. 1984, 81, 150-167.
4. Thulstrup, E. W.; Michl, J. In Spectroscopy with Polarized Light. Solute Alignment by Photoselection in Liquid Crystals, Polymers and Membranes; VCH Publishers: Deerfield Beach, 1986.
5. Thulslrup, E. W., Michl, J. In Elementary Polarization Spectroscopy, VCH Publishers: Deerfield Beach, 1989.
6. Arnold, B. R.; Schill, A. W.; Poliakov, P. V. J. Phys. Chem. A 2001, 105, 537-543.
7. Miyasaka, H.; Ojima, S.; Malaga, N. J. Phys. Chem. 1989, 93, 3380-3382.
8. Ojima, S.; Miyasaka, H.; Malaga, N. J. Phys. Chem. 1990, 94, 4147-4152.
9. Ojima, S.; Miyasaka, H.; Malaga, N. J. Phys. Chem. 1990, 94, 5834-5839.
10. Malaga, N.; Murala, Y. J. Am. Chem. Soc. 1969, 91, 3144-3152.
11. Kobayashi, T.; Yoshihara, K.; Nagakura, S. Bull. Chem. Soc. Jpn. 1971, 44, 2603-2610.
12. Gould, I. R.; Noukakis, D.; Gomez-Jahn, L.; Young, R. H.; Goodman, J. L.; Farid, S.Chem. Phys. 1993, 179, 439-456.
13. Prochorow, J.; Deperasinska, I. J. Mol. Struct. 1998, 450, 47-58.
14. Deperasinska, I.; Prochorow, J.; Dresner, J. J. Lumin. 1998, 79, 65-77.
15. Dresner, J.; Prochorow, J.; Ode, W. J. Phys. Chem. 1989, 93, 671677.
16. Findley, B. R.; Smimov, S. N.; Braun, C. L. J. Phys. Chem. A 1998, 102, 6385-6389.
17. Hayashi, M.; Yang, T.-S.; Yu, J.; Mebel, A.; Lin, S. H. J. Phys. Chem. 1997, 101, 4156-4162.
18. Jarzeba, W.; Murala, S.; Tachiya, M. Chem. Phys. Lett. 1999, 301, 347-355:
19. Wynne, K.; Reid, G. D.; Hochslrasser, R. M. J. Chem. Phys. 1996, 105, 2287-2297.
20. Okajima, S.; Lim, B. T.; Lim, E. C. Chem. Phys. Lett. 1985, 122, 82-86.
21. Lim, B. T.; Okajima, S.; Chandra, A. K.; Lim, E. C. J. Chem. Phys. 1982, 77, 3902-3909.
22. Gould, I. R.; Farid, S. J. Am. Chem. Soc. 1993, 115, 4814-4822.
23. Wegewijs, B.; Paddon-Row, M. N.; Braslavsky, S. E. J. Phys. Chem. A 1998, 102, 8812-8818.
24. Britt, B. M.; McHale, J. L.; Friedrich, D. M. J. Phys. Chem. 1995, 99, 6347-6355.
25. Markel, F.; Ferris, N. S.; Gould, I. R.; Myers, A. B. J. Am. Chem. Soc. 1992, 114, 6208-6219.
26. Kulinowski, K.; Gould, I. R.; Myers, A. B. J. Phys Chem. 1995, 99, 9017-9026.
27. Kelly, A. M. J. Phys. Chem. A 1999, 103, 6891-6903.
28. (a) Mulliken, R. S. J. Am. Chem. Soc. 1950, 72, 600.
29. (b) Mulliken, R. S. J. Am. Chem. Soc. 1950, 72, 4493.
30. Mulliken, R. S. J. Chem Phys 1951, 19, 514.
31. Mulliken, R. S. J. Am. Chem. Soc. 1952, 74, 811.
32. Mulliken, R. S. J. Chem. Phys. 1955, 23, 397.
33. Arnold, B. R.; Zaini, R. Y.; Euler, A. Spectrosc. Lett. 2000, 33, 595-614.
34. Foster, R. In Organic Charge Transfer Complexes; Academic Press: New York, 1969.
35. Mulliken, R. S.; Person, W. B. In Molecular Complexes; Wiley: New York, 1969.
36. Poliakov, P. V.; Arnold, B. R. Speclrosc. Lett. 1999, 32, 747-762.
37. HyperChem is supplied by Hypercube Inc., 1115 NW 4th Street, Gainesville, Florida 32601.
38. The oxidation potential of toluene was not recorded due to the irreversible nature of the oxidation wave. The other values were obtained from Gould, I. R.; Ege, D.; Moser, J. E.; Farid, S. J. Am. Chem. Soc. 1990, 112, 4290-4301.
39. Arnold, B. R.; Euler, A.; Fields, K.; Zaini, R. Y. J. Phys. Org. Chem. 2000, 13, 729-734.
40. Arnold, B. R.; Noukakis, D.; Farid, S.; Goodman, J. L.; Gould, I. R. J. Am. Chem. Soc. 1995, 117, 4399-4400.
41. Two different axis systems were used in the description of the TRLD data. The first axis system describes the orientation of the sample within the laboratory frame of reference. For this purpose, mutually orthogonal axes were depicted using uppercase letters (X, Y, Z). The directions of these axes within the laboratory frame were defined by the polarization direction of the photons used to excite the sample as being along the Z-axis. A second set of axes was needed to describe the molecular configurations of the donor and acceptor within each complex. Lowercase letters, (x, y, z) were used for this purpose. The origin was defined as the center of mass of TCNB, and the axes were defined as shown in Chart I. The positions of donors within the ground state complexes were then given relative to the TCNB center of mass.
42. The description of the CRIP, SSRIP, and free radical ion dynamics requires five rate constants to be determined if the currently accepted model is used (see ref 38). In the present study, the fact that the ion pair decay components were fit adequately to a single exponential is not meant to suggest they accurately portray the ion pair dynamics. The traces used in this study were recorded with optimal resolution for the determination of the anisotropy decay. As such they cannot reflect the ion pair dynamics with accuracy.
43. The relaxation time constants for several TCNB methylated benzene complexes have been recorded in acetonitrile solvent. The toluene/TCNB complex was studied in several solvents including acetonitrile and 1, 2dichloroethane. Based on the minor solvent dependence observed in the toluene complex, the complex relaxation time constants in 1, 2-DCLE can be estimated to be similar to, if perhaps a little larger than, those obtained in acetonitrile (see ref 9).
44. Fleming, G. R. In Chemical Applications of Ultrafast Spectroscopy, Oxford University Press: New York, 1986; Chapter 6.
45. 1/2. Here the anisotropy can vary between the limits 0.4 > r > -0.2. Once the angle φ is determined, the analysis of the data is identical from either perspective.
46. A clarification is required at this point. It is customary, although not always correct, to call any absorption band that appears after mixing an acceptor and donor a CT transition. For many of the complexes of interest in the present study, the transition in question may not be purely CT in nature and in some cases may not even be dominated by a CT contribution. We continue to use the term CT transition for the sake of simplicity and continuity with the established literature. It should be understood that we are simply identifying the new transition and not making a statement about its character. In due course we will be making a distinction between the pure CT TMV and the mixed CT-LE TMV that is measured herein.
47. Frey, J. E. Appl. Spectrosc. Rev. 1987, 23, 247-283.
48. The absolute value of MLE is obtained directly for the calculations of the oscillator strength, but its sign is not determined. Thus, the vector addition scheme depicted in Figure 9 is one of two possible schemes. The scheme depicted yields the best agreement with the experimentally observed values and is therefore the one adopted.
49. Birks, J. B. In Photophysics of Aromatic Molecules John Wiley and Sons: London, 1970.
50. (a) Niimura, N.; Ohashi, Y.; Saito, Y. Bull. Chem. Soc. Jpn. 1968, 41, 1815-1820.
51. (b) Lefebvre, J.; Miniewicz, A.; Kowal, R.Acta Crystallogr. 1989, C45, 1372-1376.
52. (a) Lefebvre, J.; Odou, G.; Muller, M.; Mierzejewski, A.; Luty, T. Ada Crystallogr. 1989, B45, 323-336.
53. The rotation of the donors simply changes the degree of overlap between the HOMO and HOMO-1 combinations with the acceptor orbitals. As this does not change the TMV direction within the molecular frame it is not important in the context of the current discussion.
54. 2)) where (x, y, z) are the coordinates of the donor center of mass.
55. MIX, all coincide. For any geometric relaxation process that converts the FC into the CRIP, the average position of the molecular frame with respect to the orientation axis (and the laboratory Z-axis) may change. The new position of the molecular frame is related to the previous position by a sequence of successive rotations as defined by Euler angles. For uniaxially oriented samples, such as those of interest to the present discussion, all physical rotations that cause a significant change in the orientation of the sample, on average, can be defined in terms of a rotation through a single angle. We define this angle as a topochemical angle, and the apparent rotation is described as causing a topochemical increment to the observed orientation.
56. Arnold, B. R.; Balaji, V.; Downing, J. W.; Radziszewski, J. G.; Fisher, J. J.; Michl, J. J. Am. Chem. Soc. 1991, 113, 2910-2919.
57. Sension, R. J.; Repinec, S. T.; Hochstrasser, R. M. J. Phys. Chem. 1991, 95, 2946-2948.
58. Repinec, S. T.; Sension, R. J.; Szarka, A. Z.; Hochstrasser, R. M. J. Phys. Chem. 1991, 95, 10380-10385.
59. Sension, R. J.; Repinec, S. T.; Szarka, A. Z.; Hochstrasser, R. M. J. Chem. Phys. 1993, 98, 6291-6315.