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arXiv:0810.5738 · Faraday Discussions

Two-photon coherent control of femtosecond photoassociation

Christiane P. Koch, Mamadou Ndong, Ronnie Kosloff

Published Jan 1, 2009• 21 citations
arXivHTMLPDF

Abstract

Photoassociation with short laser pulses has been proposed as a technique to create ultracold ground state molecules. A broad-band excitation seems the natural choice to drive the series of excitation and deexcitation steps required to form a molecule in its vibronic ground state from two scattering atoms. First attempts at femtosecond photoassociation were, however, hampered by the requirement to eliminate the atomic excitation leading to trap depletion. On the other hand, molecular levels very close to the atomic transition are to be excited. The broad bandwidth of a femtosecond laser then appears to be rather an obstacle. To overcome the ostensible conflict of driving a narrow transition by a broad-band laser, we suggest a two-photon photoassociation scheme. In the weak-field regime, a spectral phase pattern can be employed to eliminate the atomic line. When the excitation is carried out by more than one photon, different pathways in the field can be interfered constructively or destructively. In the strong-field regime, a temporal phase can be applied to control dynamic Stark shifts. The atomic transition is suppressed by choosing a phase which keeps the levels out of resonance. We derive analytical solutions for atomic two-photon dark states in both the weak-field and strong-field regime. Two-photon excitation may thus pave the way toward coherent control of photoassociation. Ultimately, the success of such a scheme will depend on the details of the excited electronic states and transition dipole moments. We explore the possibility of two-photon femtosecond photoassociation for alkali and alkaline-earth metal dimers and present a detailed study for the example of calcium.

DOI
10.1039/b818458e

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Photoassociation with short laser pulses has been proposed as a technique to create ultracold ground state molecules. A broad-band excitation seems the natural choice to drive the series of excitation and deexcitation steps required to form a molecule in its vibronic ground state from two scattering atoms. First attempts at femtosecond photoassociation were, however, hampered by the requirement to eliminate the atomic excitation leading to trap depletion. On the other hand, molecular levels very close to the atomic transition are to be excited. The broad bandwidth of a femtosecond laser then appears to be rather an obstacle. To overcome the ostensible conflict of driving a narrow transition by a broad-band laser, we suggest a two-photon photoassociation scheme. In the weak-field regime, a spectral phase pattern can be employed to eliminate the atomic line. When the excitation is carried out by more than one photon, different pathways in the field can be interfered constructively or destructively. In the strong-field regime, a temporal phase can be applied to control dynamic Stark shifts. The atomic transition is suppressed by choosing a phase which keeps the levels out of resonance. We derive analytical solutions for atomic two-photon dark states in both the weak-field and strong-field regime. Two-photon excitation may thus pave the way toward coherent control of photoassociation. Ultimately, the success of such a scheme will depend on the details of the excited electronic states and transition dipole moments. We explore the possibility of two-photon femtosecond photoassociation for alkali and alkaline-earth metal dimers and present a detailed study for the example of calcium.
In this work, the coherence properties of the matter is studied in the frame of photoassociation of ultracold alkali atoms by using short and ultrashort laser pulses. Ultracold can be described with temperatures below 100 microK. When energy approaches the ultracold regime, quantum properties of matter becomes visible. In this regime matter such as atoms and molecules show wave properties. Coherent control employs the wave properties of matter to steer a physical process toward a desired target. It can be implemented with coherent radiation such as laser light. In particular, femtosecond laser pulses can be shaped. They thus have become a standard tool for coherent control. Since matter shows its wave properties most clearly at ultralow temperatures, ultracold matter represents the perfect object for coherent control. In the other hand using incoherent fields on ultracold matter does not give us good opportunities to drive quantum properties of it. In this work, it is aimed to bring together ultracold and ultrafast regimes in the frame of photoassociation. Photoassociation, excitation of two colliding atoms by laser light creates very weakly bound molecules. In the first part of this study, femtosecond photoassociation experiments are simulated. In these experiments and simulations, the broad spectrum of the femtosecond pulses addressing both atomic and molecular transitions is manipulated in a way to prevent the atomic transitions and to promote the molecular transitions. Then the effect of chirp and the effect of additional phase to the pulse are examined. Excited and ground state population are monitored by carrying out quantum dynamical simulations. The driving ultrafast dipole dynamics are presented. The photoassociation rate is limited by the low initial atomic pair density at inter-nuclear separations where photoassociation is feasible. In the second part of this study, a new scheme is proposed in order to manage this low pair density by manipulating the shape resonances of the initial atom pair. A shape resonance which is a metastable state occurs when some part of the wavefunction of partial waves with J > 0 trapped by a rotational barrier shows a bound structure in the closer internuclear distances where the rest of it shows a scattering wavefunction behavior. Most of the shape resonances in alkaline and alkaline earth metals occur typically at temperatures of a few milli-Kelvin. Therefore, the thermal weight of a shape resonance at photoassociation temperatures is quite small. By applying a non-resonant laser to the system the energy of the resonant state is brought close to the energies those corresponding to the photoassociation temperatures. Thus, the thermal weight of a shape resonance is amplified and initial pair density is enhanced. This effect is studied in both adiabatic and non-adiabatic time scales with respect to the rotational period of the system, intensity effects on the resonance energy and lifetime are presented.
We investigate the dynamics of molecular photoexcitation by unchirped femtosecond laser pulses using RbCs as a model system. This study is motivated by a goal of optimizing a two-color scheme of transferring vibrationally excited ultracold molecules to their absolute ground state. In this scheme the molecules are initially produced by photoassociation or magnetoassociation in bound vibrational levels close to the first dissociation threshold. We analyze here the first step of the two-color path as a function of pulse intensity from the low-field to the high-field regime. We use two different approaches, a global one, the ``wave-packet'' method, and a restricted one, the ``level-by-level'' method, where the number of vibrational levels is limited to a small subset. The comparison between the results of the two approaches allows one to gain qualitative insights into the complex dynamics of the high-field regime. In particular, we emphasize the nontrivial and important role of far-from-resonance levels which are adiabatically excited through ``vertical'' transitions with a large Franck-Condon factor. We also point out the spectacular excitation blockade due to the presence of a quasidegenerate level in the lower electronic state. We conclude that selective transfer with femtosecond pulses is possible in the low-field regime only. Finally, we extend our single-pulse analysis and examine population transfer induced by coherent trains of low-intensity femtosecond pulses.
Weak-field coherent phase control of atomic non-resonant multiphoton excitation induced by shaped femtosecond pulses is studied theoretically in the single-cycle regime. The carrier-envelope phase (CEP) of the pulse, which in the multi-cycle regime does not play any control role, is shown here to be a new effective control parameter that its effect is highly sensitive to the spectral position of the ultrabroad spectrum. Rationally chosen position of the ultrabroadband spectrum coherently induces several groups of multiphoton transitions from the ground state to the excited state of the system: transitions involving only absorbed photons as well as Raman transitions involving both absorbed and emitted photons. The intra-group interference is controlled by the relative spectral phase of the different frequency components of the pulse, while the inter-group interference is controlled jointly by the CEP and the relative spectral phase. Specifically, non-resonant two- and three-photon excitation is studied in a simple model system within the perturbative frequency-domain framework. The developed intuition is then applied to weak-field multiphoton excitation of atomic cesium (Cs), where the simplified model is verified by non-perturbative numerical solution of the time-dependent Schrödinger equation. We expect this work to serve as a basis for a new line of femtosecond coherent control experiments.
Coherent control of femtosecond two-photon absorption in the intermediate-field regime is analyzed in detail in the powerful frequency domain using an extended 4th-order perturbative description. The corresponding absorption is coherently induced by the weak-field non-resonant two-photon transitions as well as by four-photon transitions involving three absorbed photons and one emitted photons. The interferences between these two groups of transitions lead to a difference between the intermediate-field and weak-field absorption dynamics. The corresponding interference nature (constructive or destructive) strongly depends on the detuning direction of the pulse spectrum from half the two-photon transition frequency. The model system of the study is atomic sodium, for which both experimental and theoretical results are obtained. The detailed understanding obtained here serves as a basis for coherent control with rationally-shaped femtosecond pulses in a regime of sizable absorption yields.
Quantum coherent control of ultrafast bond making and the subsequent molecular dynamics is crucial for the realization of a new photochemistry, where a shaped laser field is actively driving the chemical system in a coherent way from the thermal initial state of the reactants to the final state of the desired products. We demonstrate here coherent control over the relative yields of Mg2 molecules that are generated via photoassociation and subsequently photodriven into different groups of final states. The strong-field process involves non-resonant multiphoton femtosecond photoassociation of a pair of thermally hot magnesium atoms into a bound Mg2 molecule and subsequent molecular dynamics on electronically excited states. The branching-ratio control is achieved with linearly chirped laser pulses, utilizing the different chirp dependence that various groups of final molecular states display for their post-pulse population. Our joint experimental and theoretical study establishes the feasibility of high degree coherent control over quantum molecular dynamics that is initiated by femtosecond photoassociation of thermal atoms.
We have considered an analytical control of two-photon absorption process of atoms in the strong-field interaction regime. The experiment was performed on gaseous cesium atoms strongly interacting with a shaped laser-pulse from a femtosecond laser amplifier and a programmable pulse-shaper. When this shaped laser-pulse transfers the atomic population from the 6s ground state to the 8s excited state, we have found that both positively- and negatively-chirped laser pulses, compared with a Gaussian pulse, enhance this excitation in the strong-field regime of laser-atom interaction. This unusual phenomena is explained because the temporal shape of the laser intensity compensates the effect of dynamic Stark shift for the two-photon resonant condition to be optimally maintained. We provide analytic calculations using the strong-field phase matching, which show good agreement with the experiment.