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The Journal of Physical Chemistry A

Effect of Rotations and Shape Resonances on Photoassociation and Photoacceleration by Short Infrared Laser Pulses

Peter Backhaus, Jörn Manz, Burkhard Schmidt

Published Feb 12, 1998• 14 citations
Publisher

Abstract

A quantum dynamical description of an atomic collision pair interacting with the electric field of a short infrared laser pulse is developed. Inelastic processes in the electronic ground state are due to stimulated emission resulting in photoassociation, or absorption leading to photoacceleration. A perturbative approach based on a state space representation is compared with a numerical treatment using a grid representation in coordinate space. Special emphasis is on the role of rotations and, in particular, of shape resonances. It is shown that these quasibound states which are supported by the centrifugal barrier (for J ≠ 0) can be used as initial states to effectively populate a selected bound state with specific vibrational and rotational quantum number (photoassociation), or a partial wave of a scattering state with defined energy and rotational quantum number (photoacceleration). Simulations are carried out for the prototype H + Cl collision pair. Also the effect of averaging over initial conditions (velocity, angular momenta) is investigated for a supersonic beam experiment. For a narrow velocity distribution, we predict the presence of a resonance structure of the association and acceleration probability as a function of the mean collision energy.

DOI
10.1021/jp9800057

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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.

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Cold molecules formation by shaping with light the short-range interaction between cold atoms: photoassociation with strong laser pulses

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The paper investigates cold molecules formation in the photoassociation of two cold atoms by a strong laser pulse applied at short interatomic distances, which lead to a molecular dynamics taking place in the light-induced (adiabatic) potentials. A two electronic states model in the cesium dimer is used to analyse the effects of this strong coupling regime and to show specific results: i) acceleration of the ground state population to the inner zone due to a non-impulsive regime of coupling at short and intermediate interatomic distances; ii) formation of cold molecules in strongly bound levels of the ground state, where the population at the end of the pulse is much bigger than the population photoassociated in bound levels of the excited state; iii) the final momentum distribution of the ground state wavepacket keeping the signatures of the maxima in the initial wavefunction continuum. It is shown that the topology of the light-induced potentials plays an important role in dynamics.

arXiv:0906.1918•Jun 10, 2009•0 citations
A quantum dynamical description of an atomic collision pair interacting with the electric field of a short infrared laser pulse is developed. Inelastic processes in the electronic ground state are due to stimulated emission resulting in photoassociation, or absorption leading to photoacceleration. A perturbative approach based on a state space representation is compared with a numerical treatment using a grid representation in coordinate space. Special emphasis is on the role of rotations and, in particular, of shape resonances. It is shown that these quasibound states which are supported by the centrifugal barrier (for J ≠ 0) can be used as initial states to effectively populate a selected bound state with specific vibrational and rotational quantum number (photoassociation), or a partial wave of a scattering state with defined energy and rotational quantum number (photoacceleration). Simulations are carried out for the prototype H + Cl collision pair. Also the effect of averaging over initial conditions (velocity, angular momenta) is investigated for a supersonic beam experiment. For a narrow velocity distribution, we predict the presence of a resonance structure of the association and acceleration probability as a function of the mean collision energy.
We investigate theoretically the photoassociation process of 85Rb^{85}\mathrm{Rb}85Rb atoms driven by a short laser pulse at several millikelvins. At this temperature, the actions of the rotational barrier, weights of initial scattering states, and shape resonance emerge and have an influence on the thermally averaged photoassociation probability. The calculated thermal weighted population distribution of rotational states agrees well with photoassociation spectrum experiment. The thermally averaged photoassociation probability decreases with an increase in temperature.
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.
A (diatomic) shape resonance is a metastable state of a pair of colliding atoms quasi-bound by the centrifugal barrier imposed by the angular momentum involved in the collision. The temporary trapping of the atoms' scattering wavefunction corresponds to an enhanced atom pair density at low interatomic separations. This leads to larger overlap of the wavefunctions involved in a molecule formation process such as photoassociation, rendering the process more efficient. However, for an ensemble of atoms, the atom pair density will only be enhanced if the energy of the resonance comes close to the temperature of the atomic ensemble. Herein we explore the possibility of controlling the energy of a shape resonance by shifting it toward the temperature of atoms confined in a trap. The shifts are imparted by the interaction of non-resonant light with the anisotropic polarizability of the atom pair, which affects both the centrifugal barrier and the pair's rotational and vibrational levels. We find that at laser intensities of up to 5×1095\times 10^{9}5×109 W/cm2^22 the pair density is increased by one order of magnitude for 87^{87}87Rb atoms at 100μ100 μ100μK and by two orders of magnitude for 88^{88}88Sr atoms at 20μ20 μ20μK.
We observe the time dependence of a cold-atom collision in a pulsed photoassociation experiment. For a ggg-wave shape resonance in the 85Rb+85Rb{}^{85}\mathrm{Rb}{+}^{85}\mathrm{Rb}85Rb+85Rb system we measure the time needed to build up the resonant state by tunneling through the centrifugal barrier. Combining this with time-independent 85Rb{}^{85}\mathrm{Rb}85Rb and 87Rb{}^{87}\mathrm{Rb}87Rb photoassociation we determine the resonance energy and find evidence for the decay of the shape resonance into inelastic channels. We also determine the 85Rb+85Rb{}^{85}\mathrm{Rb}+{}^{85}\mathrm{Rb}85Rb+85Rb and 87Rb+87Rb{}^{87}\mathrm{Rb}{+}^{87}\mathrm{Rb}87Rb+87Rb C6{C}_{6}C6​ coefficient and triplet scattering lengths without relying on ab initio calculations.
Photoassociation is a possible route for the formation of chemical bonds. In this process, the binding of colliding atoms can be induced by means of a laser field. Photoassociation has been studied in the ultracold regime and also with temperatures well above millikelvins in the thermal energy domain, which is a situation commonly encountered in the laboratory. A photoassociation mechanism can be envisioned based on the use of infrared pulses to drive a transition from free colliding atoms on the electronic ground state to form a molecule directly on that state. This work takes a step in this direction, investigating the laser-pulse-driven formation of heteronuclear diatomic molecules in a thermal gas of atoms including rotational effects. Based on the assumption of full system controllability, the maximum possible photoassociation yield is deduced. The photoassociation probability is calculated as a function of the laser parameters for different temperatures. Additionally, the photoassociation yield induced by subpicosecond pulses of a priori fixed shape is compared to the maximum possible yield.
The paper investigates cold molecules formation in the photoassociation of two cold atoms by a strong laser pulse applied at short interatomic distances, which lead to a molecular dynamics taking place in the light-induced (adiabatic) potentials. A two electronic states model in the cesium dimer is used to analyse the effects of this strong coupling regime and to show specific results: i) acceleration of the ground state population to the inner zone due to a non-impulsive regime of coupling at short and intermediate interatomic distances; ii) formation of cold molecules in strongly bound levels of the ground state, where the population at the end of the pulse is much bigger than the population photoassociated in bound levels of the excited state; iii) the final momentum distribution of the ground state wavepacket keeping the signatures of the maxima in the initial wavefunction continuum. It is shown that the topology of the light-induced potentials plays an important role in dynamics.