Skip to main content
SpringerLink
Log in

Nonequilibrium Ultrafast Charge Transfer Reactions in Photoexcited Donor-Acceptor Pairs

  • Chapter
  • First Online:
Chemistry for Sustainable Development

Abstract

The ultrafast charge recombination kinetics in photoexcited donor- acceptor pairs in polar solvents has been explored. By using experimental data and theoretical modeling, the key role of medium nonequilibrium in ultrafast charge recombination has been elucidated. The influence of excitation pulse spectral characteristics as well as dynamic properties of solvent on the kinetics of such processes has been analyzed. The reorganization of high-frequency vibrational modes in hot electronic transitions has been shown to accelerate the charge recombination in the low exergonic region and to suppress it in the region of moderate exothermicity. The medium nonequilibrium can straighten the dependence of the logarithm of the charge recombination rate constant on the free energy gap to the form that can be well fitted to the experimental data. The kinetics of charge separation from the second excited state and subsequent charge recombination of the first excited state for a series of supramolecular systems have been quantitatively reproduced in the framework of stochastic multi-channel model.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 129.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 169.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 169.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Similar content being viewed by others

References

  1. Najbar J, Dorfman RC, Fayer MD (1991) Solvent relaxation effects on the kinetics of photoinduced electron transfer reactions. J Chem Phys 94:1081–1092

    Article  CAS  Google Scholar 

  2. Asahi T, Mataga N (1991) Femtosecond-picosecond laser photolysis studies on the dynamics of excited charge-transfer complexes: aromatic hydrocarbon-acid anhydride, -tetracyanoethylene, and -tetracyanoquinodimethane systems in acetonitrile solutions. J Phys Chem 95:1956–1963

    Article  CAS  Google Scholar 

  3. Walker GC, Akesson E, Johnson AE, Levinger NE, Barbara PF (1992) Interplay of solvent motion and vibrational excitation in electron-transfer kinetics: experiment and theory. J Phys Chem 96:3728–3736

    Article  CAS  Google Scholar 

  4. Tominaga K, Kliner DAV, Johnson AE, Levinger NE, Barbara PF (1993) Femtosecond experiments and absolute rate calculations on intervalence electron transfer of mixed-valence compounds. J Chem Phys 98:1228–1235

    Article  CAS  Google Scholar 

  5. Jean JM (1994) Time- and frequency-resolved spontaneous emission as a probe of coherence effects in ultrafast electron transfer reactions. J Chem Phys 101:10464–10473

    Article  CAS  Google Scholar 

  6. Tachiya M, Murata S (1994) Non-marcus energy gap dependence of back electron transfer in contact ion pairs. J Am Chem Soc 116:2434–2436

    Article  CAS  Google Scholar 

  7. Cho M, Silbey RJ (1995) Nonequilibrium photoinduced electron transfer. J Chem Phys 103:595–606

    Article  CAS  Google Scholar 

  8. Yoshihara K, Tominaga K, Nagasawa Yu (1995) Effects of the solvent dynamics and vibrational motions in electron transfer. Bull Chem Soc Jpn 68:696–712

    Article  CAS  Google Scholar 

  9. Reid PJ, Silva D, Barbara PF, Karki L, Hupp JT (1995) Electronic coherence, vibrational coherence, and solvent degrees of freedom in the femtosecond spectroscopy of mixed-valence metal dimers in H2O and D2O. J Phys Chem 99:2609–2616

    Article  CAS  Google Scholar 

  10. Barbara PF, Meyer TJ, Ratner MA (1996) Contemporary issues in electron transfer research. J Phys Chem 100:13148–13168

    Article  CAS  Google Scholar 

  11. Domcke W, Stock G (1997) Theory of ultrafast nonadiabatic excited-state processes and their spectroscopic detection in real time. Adv Chem Phys 100:1–168

    Article  CAS  Google Scholar 

  12. Ando K, Sumi H (1998) Nonequilibrium ocsillatory electron transfer in bacterial photosynthesis. J Chem Phys 102:10991–11000

    Article  CAS  Google Scholar 

  13. Yoshihara K (1999) Ultrafast intermolecular electron transfer in solution. Adv Chem Phys 107:371–401

    Article  CAS  Google Scholar 

  14. Ivanov AI, Potovoi VV (1999) Theory of non-thermal electron transfer. Chem Phys 247: 245–259

    Article  CAS  Google Scholar 

  15. Bagchi B, Gayathri N (1999) Interplay between ultrafast polar solvation and vibrational dynamics in electron transfer reactions: role of high-frequency vibrational modes. Adv Chem Phys 107:1–80

    Article  CAS  Google Scholar 

  16. Cao J (2000) Effects of bath relaxation on dissipative two-state dynamics. Chem Phys 112:6719–6724

    CAS  Google Scholar 

  17. Mataga N, Shibata Y, Chosrowjan H, Yoshida N, Osuka A (2000) Internal conversion and vibronic relaxation from higher excited electronic state of porphyrins: femtosecond fluorescence dynamics studies. J Phys Chem B 104:4001–4004

    Article  CAS  Google Scholar 

  18. Frantsuzov PA, Tachiya M (2000) Charge recombination in contact ion pairs. J Chem Phys 112:4216–4220

    Article  CAS  Google Scholar 

  19. Denny RA, Bagchi B, Barbara PF (2001) Effects of vibrational energy relaxation and reverse reaction on electron transfer kinetics and fluorescence line shapes in solution. J Chem Phys 115:6058–6071

    Article  CAS  Google Scholar 

  20. Morandeira A, Furstenberg A, Nicolet O, Pagès S, Lang B, Vauthey E (2002) Ultrafast photochemistry. Chimia 12:690–694

    Article  Google Scholar 

  21. Nicolet O, Vauthey E (2002) Ultrafast nonequilibrium charge recombination dynamics of excited donor-acceptor complexes. J Phys Chem A 106:5553–5562

    Article  CAS  Google Scholar 

  22. Koch CP, Klüner T, Kosloff R (2002) A complete quantum description of an ultrafast pump-probe charge transfer event in condensed phase. J Chem Phys 116:7983–7986

    Article  CAS  Google Scholar 

  23. Kovalenko SA, Lustres JLP, Ernsting NP, Rettig W (2003) Photoinduced electron transfer in bianthryl and cyanobianthryl in solution: the case for a high-frequency intramolecular reaction coordinate. J Phys Chem A 107:10228–10232

    Article  CAS  Google Scholar 

  24. Mataga N, Taniguchi S, Chosrowjan H, Osuka A, Yoshida N (2003) Ultrafast charge transfer and radiationless relaxation from higher excited state (S2) of directly linked Zn-porphyrin (ZP)-acceptor dyads: investigations into fundamental problems of exciplex chemistry. Chem Phys 295:215–228

    Article  CAS  Google Scholar 

  25. Fedunov RG, Feskov SV, Ivanov AI, Nicolet O, Pagès S, Vauthey E (2004) Effect of the excitation pulse carrier frequency on the ultrafast charge recombination dynamics of donor-acceptor complexes: stochastic simulations and experiments. J Chem Phys 121:3643–3656

    Article  CAS  Google Scholar 

  26. Nicolet O, Banerji N, Pages S, Vauthey E (2005) Effect of the excitation wavelength on the ultrafast charge recombination dynamics of donor−acceptor complexes in polar solvents. J Phys Chem A 109:8236–8245

    Article  CAS  Google Scholar 

  27. Fedunov RG, Ivanov AI (2005) Effect of the excitation pulse frequency on the ultrafast photoinduced electron transfer dynamics. Chem Phys 122:064501–0654508

    Google Scholar 

  28. Kuzmin MG, Soboleva IV, Dolotova EV (2008) Evolution of the reaction mechanism during ultrafast photoinduced electron transfer. J Phys Chem A 112:5131–5137

    Article  CAS  Google Scholar 

  29. Bagchi B, Oxtoby DW, Fleming GR (1984) Theory of the time development of the stokes shift in polar media. Chem Phys 86:257–267

    Article  CAS  Google Scholar 

  30. Feskov SV, Ionkin VN, Ivanov AI (2006) Effect of high-frequency modes and hot transitions on free energy gap dependence of charge recombination rate. J Phys Chem A 110:11919–11925

    Article  CAS  Google Scholar 

  31. Feskov SV, Ionkin VN, Ivanov AI, Hagemann H, Vauthey E (2008) Solvent and spectral effects in the ultrafast charge recombination dynamics of excited donor-acceptor complexes. J Phys Chem A 112:594–601

    Article  CAS  Google Scholar 

  32. Ionkin VN, Ivanov AI (2009) Numerical simulations of ultrafast charge separation dynamics from second excited state of directly linked Zn-porphyrin-imide dyads and ensuing hot charge recombination into first excited state. J Phys Chem A 113:103–107

    Article  CAS  Google Scholar 

  33. Ionkin VN, Ivanov AI (2009) Independence of the rate of the hot charge recombination in excited donor-acceptor complexes from the spectral density of high-frequency vibrations. Chem Phys 360:137–140

    Article  CAS  Google Scholar 

  34. Mikhailova VA, Ivanov AI (2007) Effect of relaxation of intramolecular high frequency vibrational mode on nonthermal electron transfer probability. Stochastic point-transition approach. J Phys Chem C 111:4445–4451

    Article  CAS  Google Scholar 

  35. Khohlova SS, Mikhailova VA, Ivanov AI (2006) Three-centered model of ultrafast photoinduced charge transfer: continuum dielectric approach. J Chem Phys 124:114507–114518

    Article  Google Scholar 

  36. Zusman LD (1980) Outer-sphere electron transfer in polar solvents. Chem Phys 49:295–304

    Article  CAS  Google Scholar 

  37. Garg S, Smyth C (1965) Microwave absorption and molecular structure in liquids. The three dielectric dispersion regions of the normal primary alcohols. J Phys Chem 69:1294–1301

    Article  CAS  Google Scholar 

  38. Risken H (1989) The Fokker-Planck equation. Springer, Berlin

    Book  Google Scholar 

  39. Yakobson BI, Burshtein AI (1980) Relaxation hindrance in nonadiabatic cage reactions. Chem Phys 49:385–395

    Article  CAS  Google Scholar 

  40. Gladkikh V, Burshtein AI, Feskov SV, Ivanov AI, Vauthey E (2005) Hot recombination of photogenerated ion pairs. J Chem Phys 123:244510-1–244510-11

    Article  Google Scholar 

  41. Gould IR, Noukakis D, Gomez-Jahn L, Goodman JL, Farid S (1993) Explanation of the driving-force dependence of return electron transfer in contact radical-ion pairs. J Am Chem Soc 115:4405–4406

    Article  CAS  Google Scholar 

  42. Mikailova VA, Ivanov AI, Vauthey E (2004) Nonequilibrium charge recombination from the excited adiabatic state of donor-acceptor complexes. J Chem Phys 121:6463–6469

    Article  Google Scholar 

  43. Wynne K, Galli C, Hochstrasser RM (1994) Ultrafast charge transfer in an electron donor–acceptor complex. J Chem Phys 100:4797–4810

    Article  CAS  Google Scholar 

  44. Gould IR, Noukakis D, Gomez-Jahn L, Young RH, Goodman JL, Farid S (1993) A quantitative relationship between radiative and nonradiative electron transfer in radical-ion pairs. J Am Chem Soc 115:3830–3831

    Article  CAS  Google Scholar 

  45. Gould IR, Noukakis D, Gomez-Jahn L, Goodman JL, Young RH, Farid S (1993) Radiative and nonradiative electron transfer in contact radical-ion pairs. Chem Phys 176:439–456

    Article  CAS  Google Scholar 

  46. Wynne K, Reid GD, Hochstrasser RM (1996) Vibrational coherence in electron transfer: the tetracyanoethylene–pyrene complex. J Chem Phys 105:2287–2297

    Article  CAS  Google Scholar 

  47. Jortner J, Bixon M (1988) Intramolecular vibrational excitations accompanying solvent-controlled electron transfer reactions. J Chem Phys 88:167–170

    Article  CAS  Google Scholar 

  48. Mataga N, Chosrowjan H, Taniguchi S, Shibata Y, Yoshida N, Osuka A, Kikuzawa T, Okada T (2002) Ultrafast charge separation from the S2 excited state of directly linked porphyrin-imide dyads: first unequivocal observation of the whole bell-shaped energy-gap law and its solvent dependencies. J Phys Chem A 106:12191–12201

    Article  CAS  Google Scholar 

  49. Morandeira A, Engeli L, Vauthey E (2002) Ultrafast charge recombination of photogenerated ion pairs to an electronic excited state. J Phys Chem A 106:4833–4837

    Article  CAS  Google Scholar 

  50. Myers Kelly A (1999) Resonance Raman intensity analysis of vibrational and solvent reorganization in photoinduced charge transfer. J Phys Chem A 103:6891–6903

    Article  Google Scholar 

  51. Mataga N, Chosrowjan H, Shibata Y, Yoshida N, Osuka A, Kikuzawa T, Okada T (2001) First unequivocal observation of the whole bell-shaped energy gap law in intramolecular charge separation from S2 excited state of directly linked porphyrin-imide dyads and its solvent-polarity dependencies. J Am Chem Soc 123:12422–12423

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was supported by the Ministry of education and science of the Russian Federation (contracts No. P1145 and No. 14.740.11.0374).

Author information

Authors and Affiliations

  1. Physical-Technical Institute, Volgograd State University, University Avenue, 100, 400062, Volgograd, Russia

    Valentina A. Mikhailova, Sergey V. Feskov, Vladimir N. Ionkin, Vladislav V. Yudanov & Anatoly I. Ivanov

Authors
  1. Valentina A. Mikhailova
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Sergey V. Feskov
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Vladimir N. Ionkin
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Vladislav V. Yudanov
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Anatoly I. Ivanov
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Valentina A. Mikhailova .

Editor information

Editors and Affiliations

  1. Faculty of Science, Dept. Chemistry, University of Mauritius, Reduit, Mauritius

    Minu Gupta Bhowon

  2. Faculty of Science, Dept. Chemistry, University of Mauritius, Reduit, Mauritius

    Sabina Jhaumeer-Laulloo

  3. Faculty of Science, Dept. Chemistry, University of Mauritius, Reduit, Mauritius

    Henri Li Kam Wah

  4. Faculty of Science, Dept. Chemistry, University of Mauritius, Reduit, Mauritius

    Ponnadurai Ramasami

Rights and permissions

Reprints and permissions

Copyright information

© 2012 Springer Science+Business Media B.V.

About this chapter

Cite this chapter

Mikhailova, V.A., Feskov, S.V., Ionkin, V.N., Yudanov, V.V., Ivanov, A.I. (2012). Nonequilibrium Ultrafast Charge Transfer Reactions in Photoexcited Donor-Acceptor Pairs. In: Gupta Bhowon, M., Jhaumeer-Laulloo, S., Li Kam Wah, H., Ramasami, P. (eds) Chemistry for Sustainable Development. Springer, Dordrecht. https://doi.org/10.1007/978-90-481-8650-1_19

Download citation

Publish with us

Policies and ethics

Search

Navigation