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Physical review. E

Nonlinear photoassociation through exotic orbits

Murilo Deliberali Forlevesi, R. Egydio de Carvalho, Emanuel F. de Lima

Published Jul 12, 2021• 4 citations
Publisher

Abstract

We investigate the effects of a particular kind of orbits, which we call exotic orbits, on the process of classical molecular photoassociation. As a starting model system, we consider the process described by the Morse potential with a time-dependent perturbation consisting of the interaction of an external laser field with the molecular dipole. When the external perturbation is turned off, the bound molecular states are classically represented by librational motion, whereas the unbound, the collisional states, are represented by unbound motion, and in both cases, the energy is a constant of motion. When the perturbation is turned on, the total energy is no longer a constant of motion and initial conditions in the unbound region can reach the bound region, and vice versa, through chaotic orbits. Alternatively, we have found that the connection between the bound and unbound sectors can be achieved through exotic orbits, which are comprised by librationlike parts, a localized chaotic region, and an unbounded constant-energy part. Thus, if a colliding atomic pair is in an exotic orbit, it penetrates a chaotic region coming from the unbound sector, subsequently performing librationlike motion, during which the molecule with constant bound energy is formed. Afterwards, the molecule returns to the chaotic region and from this region, it can either access a distinct bound energy or dissociate. We call this phenomenon, in which a metastable molecule is formed, intermittent photoassociation. We show that the key for the emergence of exotic orbits is the relatively short range of the dipole as compared to the interacting potential range. In order to further verify our results, we have considered realistic forms for the potentials and dipole functions of several molecules and found the emergence of exotic orbits, and consequently of intermittent photoassociation, for the MgLi and SrLi molecular parameters.

DOI
10.1103/physreve.104.014206

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We consider the process of photoassociation (PA) that occurs when a pair of colliding atoms interacts with a photon, thereby making a transition from the two-atom continuum to a bound molecular state. Such free-bound transitions are described by quantizing the molecule's dissociation continuum, and coupling each of these quasicontinuum (QC) levels to a similarly discrete molecular level. The correct free-atom results are recovered no later than at the end of a given calculation by taking the limit as the QC spacing tends to zero. From the quasicontinuum model, we are led to adapt the few-level and second-quantization methods of photon optics to analyze free-bound transitions. In particular, we establish the PA density parameter as nearly identical to the phase-space parameter as a Bose-Einstein condensate (BEC), illustrate the near-unit efficiency of one- and two-color photoassociation of a BEC, and develop coherent atom-molecule transitions as the matter optics version of second-harmonic generated photons. ^

•Oct 1, 1999•1 citation
We investigate the effects of a particular kind of orbits, which we call exotic orbits, on the process of classical molecular photoassociation. As a starting model system, we consider the process described by the Morse potential with a time-dependent perturbation consisting of the interaction of an external laser field with the molecular dipole. When the external perturbation is turned off, the bound molecular states are classically represented by librational motion, whereas the unbound, the collisional states, are represented by unbound motion, and in both cases, the energy is a constant of motion. When the perturbation is turned on, the total energy is no longer a constant of motion and initial conditions in the unbound region can reach the bound region, and vice versa, through chaotic orbits. Alternatively, we have found that the connection between the bound and unbound sectors can be achieved through exotic orbits, which are comprised by librationlike parts, a localized chaotic region, and an unbounded constant-energy part. Thus, if a colliding atomic pair is in an exotic orbit, it penetrates a chaotic region coming from the unbound sector, subsequently performing librationlike motion, during which the molecule with constant bound energy is formed. Afterwards, the molecule returns to the chaotic region and from this region, it can either access a distinct bound energy or dissociate. We call this phenomenon, in which a metastable molecule is formed, intermittent photoassociation. We show that the key for the emergence of exotic orbits is the relatively short range of the dipole as compared to the interacting potential range. In order to further verify our results, we have considered realistic forms for the potentials and dipole functions of several molecules and found the emergence of exotic orbits, and consequently of intermittent photoassociation, for the MgLi and SrLi molecular parameters.
We study exotic orbits in the photoassociation process by considering both the vibrational and rotational motions in a classical model. In the presence of rotational motion, the exotic orbits possess regular bound segments even when the total energy exceeds the threshold energy of the interaction potential. Such features of the exotic orbits are interpreted by introducing an effective potential. We employ Lagrangian descriptors and escape time to characterize the phase-space structure and show that exotic orbits are distributed around the stable region in the short-range phase space. We further calculate the photoassociation probability. Our work provides new insights into the dynamical mechanisms of photoassociation processes.
Introduction If, while approaching on an unbound ground-state potential, two atoms absorb a photon and couple to an excited bound molecular state, they are said to undergo photoassociation. Figure 5.1 illustrates the process. At long range electrostatic dispersion forces give rise to the ground-state molecular potential varying as C 6 / R 6 . If the two atoms are homonuclear, then a resonant dipole–dipole interaction sets up ± C 3 / R 3 excited-state repulsive and attractive potentials. Figure 5.2 shows the actual long-range excited potential curves for the sodium dimer, originating from the 2 S ½ + 2 P 3/2 and 2 S ½ + 2 P ½ separated atom states. For cold and ultracold photoassociation processes the long-range attractive potentials play the key role; the repulsive potentials figure importantly in optical shielding and suppression, the subject of Chapter 6. In the presence of a photon with frequency ω p the colliding pair with kinetic energy k B T couples from the ground-state to the attractive molecular state in a free–bound transition near the Condon point R C , the point at which the difference potential just matches ћω p . Scanning the probe laser ω p excites population of vibration–rotation states in the excited bound potential and generates a free–bound spectrum. This general class of measurements is called photoassociative spectroscopy (PAS) and can be observed in several different ways. The observation may consist of bound-state decay by spontaneous emission, most probably as the nuclei move slowly around the outer turning point, to some distribution of continuum states on the ground potential controlled by bound–free nuclear Franck–Condon overlap factors.
We experimentally investigate various processes present in the photoassociative interaction of an ultracold atomic sample with shaped femtosecond laser pulses. We demonstrate the photoassociation of pairs of rubidium atoms into electronically excited, bound molecular states using spectrally cut femtosecond laser pulses tuned below the rubidium D1 or D2 asymptote. Time-resolved pump-probe spectra reveal coherent oscillations of the molecular formation rate, which are due to coherent transient dynamics in the electronic excitation. The oscillation frequency corresponds to the detun-ing of the spectral cut position to the asymptotic transition frequency of the rubidium D1 or D2 lines, respectively. Measurements of the molecular photoassociation signal as a function of the pulse energy reveal a non-linear dependence and indicate a non-perturbative excitation process. Chirping the association laser pulse allowed us to change the phase of the coherent transients. Furthermore, a signature for molecules in the electronic ground state is found, which is attributed to molecule formation by femtosecond photoassociation followed by spontaneous decay. In a subsequent article [A. Merli et al., submitted] quantum mechanical calculations are presented, which compare well with the experimental data and reveal further details about the observed coherent transient dynamics.
The establishment of robust laser-cooling techniques for the formation of ultracold atoms has provided a test-bed for low-temperature science, with scattering events changing character from incoherent thermal interactions to coherent quantum mechanical events. A natural extension is the pursuit of ultracold molecules in prescribed low-energy internal states. Atomic cooling techniques, however, do not generalize to the molecular regime due to the complex energy-level structure afforded by its extra degrees of motion. An indirect approach to ultracold molecule formation - photoassociation using ultrafast laser pulses - is the focus of this thesis. A broadband field associates atom pairs into a localized molecular wavepacket that evolves within the attractive excited-state potential. A suitably timed dump pulse may thus be applied to stabilize population into deeply bound ground vibrational states. This strategy may be generalized to any species whose spectroscopy matches the pulse spectrum, and offers a coherent population transfer scheme that does not require precise knowledge of the system. This thesis presents experiments using high-energy photoassociation pulses applied to ultracold rubidium atoms. The pulses quench the background ground-state molecular population but form bound dimers within the excited state. A pump-probe experiment was designed to chart the excited-state dynamics; however, the oscillations predicted by theoretical calculations were not evident in the molecular signal. The nature of the dynamics is expected to be strongly dependent on the initial state of the atom pairs addressed by the ultrafast pulse: a bound molecular population provides an additional candidate to free atoms. A spectroscopic measurement characterizes these bound molecules and identifies their formation mechanism. A subsequent experiment provides evidence that the predominant contributor to the pump-probe signal is the unbound initial population. The consequences with regard to both the observation of excited-state dynamics and the subsequent application of a dump pulse are discussed.
Photoassociation is a process by which two cold, trapped atoms can be optically excited during a collision to make a vibrational level of an excited electronic state of a molecular dimer. High-resolution photoassociation spectra are now well-known for most alkali dimers. The upper level normally decays by spontaneous emission to a number of final molecular levels, bound and unbound. A laser of a second color can be used to stimulate a transition from the upper level to a particular ground state vibrational level. Such a Raman photoassociation process can be used to form translationally cold molecules in a cold atomic gas or a Bose-Einstein condensate. Coupled channels scattering calculations show that the collisional rate coefficient for coherent production of molecules in specific target states, >10−10cm3/s,> 10^{-10} cm^{3}/s,>10−10cm3/s, can greatly exceed the rate coefficient for forming products due to excited state spontaneous decay. This implies the feasibility of rapid coherent conversion of atom pairs in a condensate to molecules on a time scale short compared to the trap oscillation time. The untrapped molecules can form a coherent molecular beam. We will examine the prospects for the experimental realization of photoassociative molecule formation in cold alkali gases or condensates.
We consider the process of photoassociation (PA) that occurs when a pair of colliding atoms interacts with a photon, thereby making a transition from the two-atom continuum to a bound molecular state. Such free-bound transitions are described by quantizing the molecule's dissociation continuum, and coupling each of these quasicontinuum (QC) levels to a similarly discrete molecular level. The correct free-atom results are recovered no later than at the end of a given calculation by taking the limit as the QC spacing tends to zero. From the quasicontinuum model, we are led to adapt the few-level and second-quantization methods of photon optics to analyze free-bound transitions. In particular, we establish the PA density parameter as nearly identical to the phase-space parameter as a Bose-Einstein condensate (BEC), illustrate the near-unit efficiency of one- and two-color photoassociation of a BEC, and develop coherent atom-molecule transitions as the matter optics version of second-harmonic generated photons. ^