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Physical Review A

Short-pulse chirped adiabatic population transfer in diatomic molecules

Shimshon Kallush, Y. B. Band

Published Feb 28, 2000• 49 citations
Publisher

Abstract

Using the concept of light-induced potentials introduced by Garraway and Suominen [Phys. Rev. Lett. 80, 932 (1998)], we study alternative schemes of adiabatic population transfer in a diatomic molecule from the lowest vibrational level of the ground electronic state to the lowest vibrational level of a third electronic state via allowed optical transitions from the ground and third electronic states to a second electronic state. Our chirped-pulse rapid adiabatic passage scheme is implemented with short-duration optical pulses, and can be understood in terms of ``road design engineering'' of the light-induced time-dependent adiabatic potential upon which the dynamics occurs. We explicitly show that complete adiabatic vibronic population transfer occurs using chirped picosecond-duration pulses in the sodium dimer example.

DOI
10.1103/physreva.61.041401

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The Journal of Chemical Physics•Nov 14, 2002•15 citations
Using the concept of light-induced potentials introduced by Garraway and Suominen [Phys. Rev. Lett. 80, 932 (1998)], we study alternative schemes of adiabatic population transfer in a diatomic molecule from the lowest vibrational level of the ground electronic state to the lowest vibrational level of a third electronic state via allowed optical transitions from the ground and third electronic states to a second electronic state. Our chirped-pulse rapid adiabatic passage scheme is implemented with short-duration optical pulses, and can be understood in terms of ``road design engineering'' of the light-induced time-dependent adiabatic potential upon which the dynamics occurs. We explicitly show that complete adiabatic vibronic population transfer occurs using chirped picosecond-duration pulses in the sodium dimer example.
This paper describes an investigation into the process of adiabatic passage by light-induced potentials (APLIP), which was previously suggested as a method for employing two strong picosecond laser pulses to transfer the population between two electronic states. We have extended earlier numerical studies in order to assess the feasibility of an experimental implementation of the APLIP concept. APLIP has been modeled in a three-level model system based on Na2 with chirped pulses, using laser parameters available from a typical chirped pulse amplified Ti:sapphire laser. The model showed that the APLIP process remains essentially unchanged for chirped pulses of equal magnitude and the opposite, or equal and positive sign of chirp as compared to the transform-limited case. We also examined the case of additional electronic states by introduction of a fourth state that lies close to the "target," i.e., final, state. The investigation showed that there are circumstances in which a significant fraction of the population gets transferred to this state which will disrupt the APLIP process. However, by switching to this fourth state as the target state in an experiment, good transfer efficiency is recovered. The results of the extension of the original APLIP modeling to chirped pulses and additional electronic states indicate that an APLIP experimental realization should be feasible in Na2.
Summary form only given. We propose a method for achieving highly efficient transfer between the vibrational states in a diatomic molecule. The process is mediated by strong laser pulses and can be understood in terms of light-induced potentials. Light-induced potentials were also key to understanding APLIP (adiabatic passage by light induced potentials), where a wave packet is guided from one ground vibrational state to another. However, in the new process we show how to target specific vibrational states with strong short pulses. In addition to describing a specific molecular system, our results show how, in general, one can manipulate the populations of the different quantum states in double well systems.
We study the dynamics of two-photon nonresonant electronic excitation of diatomic molecules driven by chirped pulses. While the majority of the experimental results address the role of the chirp for fixed pulse bandwidth, we analyze the possibility of selective excitation for fixed time, as a function of the pulse bandwidth, depending on the sign of the chirp. With strong picosecond pulses and positive chirp it is shown that the dynamics always prepare the molecule in the ground vibrational level of the excited electronic state. The robustness of the dynamics inherits the properties of an effective Landau–Zener crossing. For negative chirp the final state is very sensitive to the specific pulse bandwidth. The dynamics of the system follow a complex convoluted behavior, and the final state alternates between low vibrational levels of the excited electronic state and excited vibrational levels of the ground potential, which become increasingly more excited with increasing bandwidth. The final electronic populations follow a double-period oscillatory behavior. We present a model based on sequential independent crossings which correlates the long-oscillation period with changes in the final vibrational state selected. We show that the short-oscillation period is related with nonadiabatic effects that give rise to fast dynamic Rabi flipping between the electronic states, providing only information of the field–molecule effective coupling. Although the short-oscillation period partially masks the expected results of the final populations, we show that it is still possible to retrieve information from the long-oscillation period regarding the frequencies of the electronic potentials. In order to do so, or in order to control the outcome of the dynamics, it is necessary to perform experiments scanning very different pulse bandwidths, and we propose a possible experimental implementation. All the numerical results of the paper are calculated for a model of the Na2 dimer.
Efficient population transfer by adiabatically chirping through a multiphoton resonance in microwave driven and kicked Rydberg atoms has recently been reported both experimentally and theoretically. Here we report on our simulations in which we have exploited this mechanism to vibrationally excite a diatomic molecule up to |ν = 4, J from the ground state by chirping through a four-photon resonance condition. This is an efficient means of population transfer, which is an alternative to the ladder climbing scheme requiring chirping through a sequence of states in the correct order. We discuss and compare one-dimensional quantum and classical models where there is no rotational degree of freedom. This comparison suggests that for the lowest laser intensity we consider, the process is classically forbidden and the transition occurs through tunnelling. We show that for larger peak intensities, the transfer can be looked upon as a classical transition in phase space, similar to that observed in the atomic case. We extend our simulations to fully three-dimensional quantum calculations and investigate the effect of coupling between different rotational pathways. We finally discuss the effect of thermal averaging over the initial J-states using a temperature for which the first few rotational levels inside the ν = 0 manifold are populated.
Enhanced population transfer from the lowest to the highest level in the three-state ladder 5s->5p->5d of the rubidium atom by frequency swept ultra short laser pulses is observed if the frequency sweep first makes the pulse resonant with the 5s->5p transition, and later with the 5p->5d transition. With this intuitive scheme it is possible to achieve complete population inversion via the intermediate level by two successive adiabatic passages. Complete inversion is also obtained by a {open_quote}counterintuitive{close_quote} direction of the frequency-sweep, in which case population of the intermediate level during the pulse is strongly reduced. The atomic system can be seen as a model system for multistep vibrational excitation in an anharmonic molecular potential.
A new scheme of controlling molecular processes by a sequence of linearly chirped pulses is proposed and is applied to selective excitation of an energy level among closely lying ones and to complete electronic excitation of a diatomic molecule. The basic idea is quite different from the conventional ones utilizing chirped pulses in the sense that the present one does not rely on the idea of adiabatic rapid passage at all, but tries to control basic nonadiabatic transitions explicitly. Control of molecular processes can be achieved by controlling nonadiabatic transitions among Floquet (or dressed) states with use of the interference effects. The scheme can be formulated with use of the analytical theories of nonadiabatic transitions, and the proper control parameters can be estimated theoretically. Numerical demonstrations are provided to confirm the robustness of the method in comparison with the other conventional ones. Namely, the present scheme is shown to be stable against the variation of pulse area, complete and selective in population transfer, and fast to accomplish the transition. It is expected that the method can be applied to general multilevel systems and various types of wave packet dynamics. Its experimental realizability can also be expected, since linear chirping can now be relatively easily realized and manipulated.