Sequences for controlling laser excitation with femtosecond three-pulse four-wave mixing

Abstract

Three-pulse four-wave mixing (FWM) is used here to study and control laser excitation processes. For general laser excitation processes, after a molecule interacts resonantly with a laser pulse, the molecule has a probability of being in the ground or in the excited state. Control over this process depends on the phase and amplitude of the electric fields that interact with the molecular system. Here we show how three-pulse FWM can be used to control the excitation of iodine molecules. Depending on the time delay between the first two pulses, the observed signal reflects the dynamics of the ground or excited state. A theoretical formalism based on the density matrix formulation is presented and solved for a four-level system. Experiments are found to be in excellent agreement with the theory. The influence of linear chirp on three-pulse FWM experiments is explored. Spectrally dispersed three-pulse FWM is found to be extremely useful for studying the effect of chirp on laser excitation of molecular systems. Experimental demonstrations of these effects are included.

References

1. S. A. Passino, Y. Nagasawa and G. R. Fleming, J. Chem. Phys., 1997, 107, 6094.
2. W. P. de Boeij, M. S. Pshenichnikov and D. A. Wiersma, Annu. Rev. Phys. Chem., 1998, 49, 99.
3. M. N. Yang and G. R. Fleming, J. Chem. Phys., 1999, 110, 2983.
4. Y. J. Yan, L. E. Fried and S. Mukamel, J. Phys. Chem., 1989, 93, 8149.
5. E. J. BrownI. PastirkB. I. GrimbergV. V. LozovoyM. DantusJ. Chem. Phys. accepted..
6. R. J. Gordon and S. A. Rice, Annu. Rev. Phys. Chem., 1997, 48, 601.
7. P. Gaspard and I. Burghardt, in Chemical Reactions and Their Control on the Femtosecond Timescale, Wiley, New York, 1997.
8. A. Assion, T. Baumert, M. Bergt, T. Brixner, B. Kiefer, V. Seyfried, M. Strehle and G. Gerber, Science, 1998, 282, 919.
9. Y. R. Shen, The Principle of Nonlinear Optics, Wiley, New York, 1984.
10. S. Mukamel, Principles of Nonlinear Optical Spectroscopy, Oxford University Press, New York, 1995, ch. 5.
11. I. Pastirk, V. V. Lozovoy, I. Grimberg, E. J. Brown and M. Dantus, J. Phys. Chem A, submitted.
12. E. J. Brown, Q. Zhang and M. Dantus, J. Chem. Phys., 1999, 110, 5772.
13. V. V. Lozovoy, I. Pastirk, E. J. Brown, B. I. Grimberg and M. Dantus, in preparation.
14. P. H. Vaccaro, in Degenerate Four-Wave Mixing (DFWM) Spectroscopy, ed. E. Hirota, R. W. Field, J. P. Maier and S. Tsuchiya, Blackwell Scientific Publications Ltd. for Physical Chemistry Division of IUPAC, London, 1997.
15. S. Mukamel, M. Cho and G. R. Fleming, J. Chem. Phys., 1993, 98, 5314.
16. R. W. Boyd, Nonlinear Optics, Academic Press, San Diego, 1992.
17. M. S. Pshenichnikov, W. P. d. Boeij and D. A. Wiersma, Phys. Rev. Lett., 1996, 76, 4701.
18. Y. Prior, Appl. Opt., 1980, 19, 1741.
19. J. A. Shirley, R. J. Hall and A. C. Eckbreth, Opt. Lett., 1980, 5, 380.
20. M. Schmitt, G. Knopp, A. Materny and W. Kiefer, Chem. Phys. Lett., 1997, 270, 9.
21. M. Schmitt, G. Knopp, A. Materny and W. Kiefer, Chem. Phys. Lett., 1997, 280, 339.
22. S. Meyer, M. Schmitt, A. Materny, W. Kiefer and V. Engel, Chem. Phys. Lett., 1999, 301, 248.
23. J. Tellinghuisen, J. Quant. Spectrosc. Radiat. Transfer, 1978, 19, 149.
24. M. Dantus, R. M. Bowman and A. H. Zewail, Nature (London), 1990, 343, 737.
25. M. Gruebele, G. Roberts, M. Dantus, R. M. Bowman and A. H. Zewail, Chem. Phys. Lett., 1990, 166, 459.
26. R. J. LeRoy, J. Chem. Phys., 1970, 52, 2683.
27. V. V. Lozovoy, I. Pastirk and M. Dantus, J. Chem. Phys., submitted.
28. W. M. Zhang, V. Chernyak and S. Mukamel, J. Chem. Phys., 1999, 110, 5011.
29. T.-S. Yang, R. Zhang and A. Myers, J. Chem. Phys., 1994, 100, 8573.
30. M. Sterling, R. Zadoyan and V. A. Apkarian, J. Chem. Phys., 1996, 104, 6497.
31. C. J. Bardeen, J. Che, K. R. Wilson, V. Yakovlev, V. A. Apkarian, C. C. Martens, R. Zadoyan, B. Kohler and M. Messin, J. Chem. Phys., 1997, 106, 8486.
32. V. Yakovlev, C. J. Bardeen, J. Che, J. Cao and K. R. Wilson, J. Chem. Phys., 1998, 108, 2309.
33. V. V. Lozovoy, S. A. Antipin, F. E. Gostev, A. A. Titov, D. G. Tovbin, O. M. Sarkisov, A. S. Vetchinkin and S. Y. Umanskii, Chem. Phys. Lett., 1998, 284, 221.
34. V. V. Lozovoy, A. A. Titov, F. E. Gostev, D. G. Tovbin, S. A. Antipin, S. Y. Umanskii and O. M. Sarkisov, Chem. Phys. Rep., 1998, 17, 1267.
35. V. V. Lozovoy, O. M. Sarkisov, A. S. Vetchinkin and S. Y. Umanskii, Chem. Phys., 1999, 243, 97.
36. B. I. Grimberg, V. V. Lozovoy and M. Dantus, in preparation.
37. B. Broers, H. B. van Linden van den Heuvell and L. D. Noordam, Phys. Rev. Lett., 1992, 69, 2062.
38. J. S. Melinger, S. R. Gandhi, A. Hariharan, J. X. Tull and W. S. Warren, Phys. Rev. Lett., 1992, 68, 2000.
39. J. S. Melinger, S. R. Gandhi, A. Hariharan, D. Goswami and W. S. Warren, J. Chem. Phys., 1994, 101, 6439.
40. Y. B. Band and O. Magnes, Phys. Rev. A., 1994, 50, 584.
41. N. F. Scherer, A. J. Ruggiero, M. Du and G. R. Fleming, J. Chem. Phys., 1990, 93, 856.