Effect of propagation on pulsed four-wave mixing P. Weisman, A. D. Wilson-Gordon, and H. Friedmann Department of Chemistry, Bar-Ilan University, Ramat Gan 52900, Israel Received 1 November 1999; published 17 April 2000 We examine the effect of propagation on the resonance Rabi sideband of the four-wave mixing FWM spectrum, obtained when short temporally displaced pump and probe pulses interact with an optically thick medium of two-level atoms. We find that the dependence of the time-integrated FWM signal on the pump- probe delay is considerably altered by propagation. In particular, the logarithm of the FWM signal, for the case where the probe precedes the pump, deviates from linearity and may even increase over a range of values. An explanation is given in terms of the overlap of the pump envelope with the coherent response of the atomic system to the probe, both of which are modified on propagation. PACS numbers: 42.65.Hw, 42.50.Gy, 42.50.Md I. INTRODUCTION The steady-state excitation four-wave-mixing FWM spectrum obtained when a two-level system interacts with a coherent pump of arbitrary intensity and fixed frequency 1 and a weak probe of varying frequency 2 is symmetrical and consists of three peaks 1,2. In addition to the central peak at 2 = 1 , there are two Rabi sidebands at 2 = 1 1 where the pump generalized Rabi frequency 1 =( 1 2 +4 | V 1 2 | ) 1/2 is determined by the pump detuning from resonance 1 = ba - 1 and its Rabi frequency 2 V 1 =E 1 / . In the limit of large detuning 1 2 | V 1 | one of the peaks is situated near the resonance frequency 2 ba and the other near the three-photon scattering TPSfre- quency 2 2 1 - ba . However, a completely different picture emerges when the cw pump and probe fields are re- placed by short pulses 3,4. We have shown for temporally overlapping pulses 3, that the spectrum becomes asym- metrical with the relative widths and heights of the Rabi sidebands determined mainly by the linewidths of the laser pulses. We have also shown for temporally nonoverlapping pulses 4that the spectrum becomes extremely asymmetri- cal and that only the sideband near the resonance frequency survives, for the case where the probe precedes the pump. For the opposite case where the pump precedes the probe, no FWM spectrum is obtained at all. It should be noted that these results hold provided the the pump and probe durations D 1 and D 2 are much shorter than the transverse relaxation time T 2 and also shorter than the time delay between the pump and probe t 0 ( t 0 0 implies that the probe precedes the pump. We also showed 4that T 2 can be determined from the slope of the semilog plot of the FWM intensity, near the resonance sideband, versus t 0 for t 0 0. In this paper, we will study the effect of propagation in a thick atomic medium on the FWM spectrum. In particular, we will show that as propagation proceeds, the semilog plot which is initially linear begins to deviate from linearity and may even changes the sign of its slope for a range of values of t 0 . This asymmetry of the resonance peak with respect to the pump-probe time delay is well known for the case of degen- erate FWM DFWMusing weak, short, resonant pulses ( 1 = 2 = ba ) in optically thin samples 5. DFWM has been widely applied to femtosecond real-time probing of gas-phase chemical reactions, including the the study of transition-state dynamics 6, and also in studies of liquid and solid systems 7,8where the dephasing time T 2 has been determined from the dependence of the time-integrated FWM on the pump-probe time delay. By varying the pulse sequences, it is also possible to measure the population de- cay time T 1 6. Variations of FWM such as coherent time- resolved anti-Stokes Raman spectroscopy CARS9and time-resolved transient-grating TGtechniques 10have been used to explore the molecular dynamics both popula- tions and coherencesin gas-phase systems ranging from single atoms to large polyatomic molecules. The majority of theoretical treatments of pulsed FWM and its variants, in gas-phase systems unlike those in solids 8, include neither saturation nor propagation effects and are based on perturbation theory 11. Studies of saturation effects include a nonperturbational approach to picosecond experiments using spatial and frequency gratings 12and an extension to the transient regime 13of the classic nonper- turbative steady-state theory pf DFWM, developed by Abrams and Lind 14. Propagation effects in DFWM for time-delayed pulses have been studied both experimentally and theoretically by Kinrot and Prior 15for gaseous alkali atoms. Their theoretical treatment is a combination of Ya- jima and Taira’s 5perturbative ‘‘standard model’’ of DFWM in thin slabs and Crisp’s theory 16of propagation of 0pulses, and is therefore only valid for weak pump pulses. In the present paper, we are interested in the effect of propagation on the asymmetry, with respect to pump-probe time delay, of the Rabi sideband near the resonance fre- quency in the FWM excitation spectrum 3. Our treatment is based on the numerical solution of the Maxwell-Bloch equa- tions for a short pump pulse of arbitrary intensity and detun- ing and a short, weak probe pulse. Several of Kinrot and Prior’s conclusions 15will be of relevance here. For ex- ample, they found that the DFWM signal becomes signifi- cant, on propagation, even when the pump precedes the probe. This has also been observed in solid-state DFWM experiments 17and has been explained by a wide variety of mechanisms appropriate to the particular system being studied. Kinrot and Prior also found that the slope of the In of the FWM signal as a function of the pump-pulse delay PHYSICAL REVIEW A, VOLUME 61, 053816 1050-2947/2000/615/0538166/$15.00 ©2000 The American Physical Society 61 053816-1