Coherent control of atomic and molecular scattering relies on the preparation of colliding particles in superpositions of internal states, establishing interfering pathways that can be used to tune the outcome of a scattering process. However, the incoherent addition of different partial wave contributions to the integral cross-sections, commonly encountered in systems with complex collisional dynamics, poses a significant challenge, often limiting the control. This work demonstrates that time-reversal symmetry can be used to overcome these limitations by constraining the relation between the S-matrix elements. For example, the preparation of a superposition of two states related by the time-reversal superposition can provide extensive control for transitions to a time-reversal invariant final state, such as the J = 0, M = 0. Using the example of ultracold O2-O2 scattering, we show that for such states coherent control is robust against short-range dynamical complexity. Furthermore, the time-reversal symmetry also protects the control against a distribution of collisional energies. Beyond the ultracold regime, we observe significant differences in the controllability of crossed-molecular beam vs trap experiments with complete control achievable in the former case at any temperature, emphasizing the cooperative role of time-reversal and permutation symmetries in maintaining control at any temperature. These results open new avenues for the coherent control of complex inelastic collisions and chemical reactions both in and outside of the ultracold regime.

Interference is widely regarded as a foundational attribute of quantum mechanics. However, for a given experimental arrangement, interference can either contribute or not contribute to the outcome depending upon the basis in which it is measured. This observation is both foundational and particularly relevant to coherent control of molecular processes, an approach based upon quantum interference. Here, we address this issue and its relevance to controlling molecular processes via the “coherent control scattering (CCS) matrix,” a formalism that allows for an analysis of modifications in an interference structure resulting from a change of basis. This analysis reveals that the change in the interference structure can be attributed to the non-commutativity of the transformation matrix with the CCS matrix and the non-orthogonality of the transformation. Additionally, minimal interference is shown to be associated with the CCS eigenbasis and that the Fourier transform of the eigenvectors of the CCS matrix provides the maximal interference and hence the best coherent control. The change of controllability through a change of basis is illustrated with an example of 85Rb+ 85Rb scattering. In addition, the developed formalism is applied to explain recent experimental results on He + D2 inelastic scattering demonstrating the presence or absence of interference depending on the basis.

We consider the coherent control of ultracold molecule-molecule scattering, impacted by a dense set of rovibrational resonances. To characterize the resonance spectrum, a rudimentary model based on multichannel quantum defect theory has been used to study the control of the scattering cross section and the reaction rate. Complete control around resonance energies is shown to be possible, but thermal averaging over a large number of resonances significantly reduces the extent of control of reaction rates related to the random distribution of optimal control parameters between resonances. We show that measuring the extent of coherent control could be used to extract meaningful information about the relative contribution of direct scattering versus collision complex formation, as well as about the statistical regime.

Quantum coherent control of bimolecular collisions beyond the ultracold regime can face a major challenge due to the incoherent addition of different partial wave contributions to the total scattering cross section. These contributions become increasingly numerous as the collision energy increases, leading to a loss of overall control. Here, we overcome this limitation by leveraging the recently discovered Partial Wave Phase Locking (PWPL) effect, which synchronizes the oscillations of all partial wave contributions. By using rigorous quantum scattering calculations, we demonstrate that PWPL enables coherent control of spin exchange in ion-atom collisions, far outside the ultracold regime, even with as many as 5000 partial wave contributions. The predicted extent of control is sufficient to be measurable in cold atom-ion hybrid experiments.

The optical theorem is a fundamental aspect of quantum scattering theory. Here, we generalize this theorem to the case where the incident scattering state is a superposition of internal states of the collision partners, introducing additional interference contributions and, e.g., providing a route to control the total integral cross section. As in its standard form, forward scattering plays an essential role in the generalized optical theorem, but with interference terms being related to the inelastic forward scattering amplitudes between states in the initial superposition. Using the resultant control index, we show that extensive control is possible over ultracold collisions of oxygen molecules in their rovibrational ground states, and of 85Rb-85Rb collisions, promising systems for the first experimental demonstration of the quantum interference control of the total scattering cross section.

We show that the cross sections for a broad range of resonant inelastic processes accompanied by excitation exchange (such as spin exchange, Forster resonance, or angular momentum exchange) exhibit a near-threshold scaling E-Delta m12, where E is the collision energy, Delta m(12) = m(1)' + m(2)' - m(1) - m(2), and m(i) and m(i)' are the initial and final angular momentum projections of the colliding species (i = 1, 2). In particular, the inelastic cross sections for Delta m(12) = 0 transitions display an unconventional E-0 scaling similar to that of elastic cross sections, and their rates vanish as T Delta m12+1/2. For collisions dominated by even partial waves (such as those of identical bosons in the same internal state) the scaling is modified to sigma(inel) proportional to E Delta m12+1 if Delta m(12) is odd. We present accurate quantum scattering calculations that illustrate these modified threshold laws for resonant spin exchange in ultracold Rb + Rb and O-2 + O-2 collisions. Our results illustrate that the well-known k(-1) threshold scaling of inelastic cross sections only applies to exothermic, rather than resonant, inelastic processes.

The 53rd Annual Meeting of the APS Division of Atomic, Molecular and Optical Physics will take place from May 30 – June 3, 2022 in Orlando, Fl, USA. Virtual Presenter Help Desk

The optical theorem is a fundamental aspect of quantum scattering theory. Here, we generalize this theorem to the case where the incident scattering state is a superposition of internal states of the collision partners, introducing additional interference contributions and, e.g., providing a route to control the total integral cross section. As in its standard form, forward scattering plays an essential role in the multichannel optical theorem, but with interference terms being related to the inelastic forward scattering amplitudes between states in the initial superposition. Using the resultant control index, we show that extensive control is possible over ultracold collisions of oxygen molecules in their rovibrational ground states, and of Rb-85-Rb-85 collisions, promising systems for the experimental demonstration of the quantum interference control of the total scattering cross section.

The exquisite control of diluted atomic vapors that can be achieved using electromagnetic (em) fields triggered the overwhelming development of researches on ultracold (T<<1millikelvin) quantum gases through laser cooling and trapping, opening ways to amazing applications in quantum technologies. For a composite system like a molecule under such ultracold conditions, the additional control of the internal degrees of freedom has also been recently demonstrated [1] with cw visible, microwave, and radio radiation frequencies for electronic, rotational, and hyperfine transitions, respectively. Vibrational transitions could be addressed with THz transitions, as an attractive path for controlling the interatomic interactions and creating ultracold gases of a wide class of diatomic molecules in their absolute ground state. More specifically, THz radiation can induce a coupling between the bound level of a pair of trapped ultracold ground-state atoms and a loosely-bound vibrational level of the related molecular electronic ground state. This coupling, generated by the intrinsic permanent electric dipole moment of a heteronuclear atomic pair (RbSr in the present work), is related to a specific spectroscopic feature of the atomic pair dressed by the THz field, the Laser Assisted Self-Induced Feshbach Resonance (LASIFR) [2] . In analogy with magnetic Feshbach resonance, the scattering length can be controlled by tuning the THz radiation frequency around a LASIFR (see Fig (a)).

We show that quantum interference-based coherent control is a highly efficient tool for tuning ultracold molecular collision dynamics that is free from the limitations of commonly used methods that rely on external electromagnetic fields. By varying the relative populations and phases of initial coherent superpositions of degenerate molecular states, we demonstrate complete coherent control over integral scattering cross sections in the ultracold s-wave regime of both the initial and final collision channels. The proposed control methodology is applied to ultracold O_{2}+O_{2} collisions, showing extensive control over s-wave spin-exchange cross sections and product branching ratios over many orders of magnitude.

We have studied the formation of ultracold RbSr molecules with laser pulses. After discussing the advantages of the Mott insulator phase for the control with pulses, we present two classes of strategies. The first class involves two electronic states. Two extensions of stimulated Raman adiabatic passage (STIRAP) for multilevel transitions are used: alternating STIRAP (A-STIRAP) and straddle STIRAP (S-STIRAP). Both transfer dynamics are modeled and compared. The second class of strategies involves only the electronic ground state and uses infrared (IR) and terahertz (THz) pulses. The molecular bond is first created by the application of a THz chirped pulse or $\ensuremath{\pi}$-pulse. Subsequently, the molecules are transferred to their rovibrational ground level using IR pulses. For this last step, different optimized pulse sequences that were obtained through optimal control techniques have been studied. The relative merits of these strategies in terms of efficiency and robustness are discussed with respect to the experimental feasibility based on present laser technologies.

Fundamental entanglement related challenges have prevented quantum interference-based control (i.e. coherent control) of collisional cross sections from being implemented in the laboratory. Here, differential cross sections for reactive scattering at low temperatures are shown to provide a unique opportunity to display such interference-based control by forming coherent superpositions of degenerate rotational states of reactant molecules |jmi with different m. In particular, we identify and quantify a unique signature of coherent control in reactive scattering with applications to F + H2 ! H + HF and HF + D F + HD ! HD + F at 11 K. Control is shown to be extensive.

We propose a new kind of Feshbach Resonance (FR) : the Laser-Assisted Self-Induced Feshbach Resonance (LASIFR), applicable for all mixtures of ultracold atoms. The interspecies scattering length characterizing elastic collisions, a key property for many applications of ultracold quantum gases, can be controlled by a LASIFR through the laser intensity and the frequency. It can be also used for the formation of ultracold polar molecules.

La thèse se positionne dans le domaine des molécules ultra-froides, c’est-à-dire des molécules qui ont des vitesses correspondant à des températures de l’ordre du µK. L’obtention de gaz dilués moléculaires à ces températures peut ouvrir la porte à des applications importantes en simulation ou en informatique quantique. La thèse s’intéresse plus particulièrement à la formation de molécules dipolaires électriques et magnétiques. Celles-ci sont présagées pour être un système idéal dans l’optique d’un simulateur quantique du système réseau-spin, permettant de décrire le magnétisme dans les solides. Nous avons choisi l’exemple de la molécule RbSr qui fait l’objet actuellement d’une expérience à Amsterdam. Nous avons donc exploré plusieurs alternatives basées sur l’emploi de laser pour la formation de molécules RbSr ultra-froides Nous avons d’abord considéré la photoassociation dont le principe est de coupler l’état de collision initial avec un état rovibrationnel d’un état électronique excité. L’étape d’émission spontanée qui suit forme des molécules dans l’état électronique fondamental. Nous avons également considéré le problème des pertes supplémentaires d’atomes lorsque le laser de photoassociation est intense et focalisé, mises en évidence dans une expérience à Bangalore. Dans la suite de la thèse, nous avons exploré des méthodes cohérentes. Nous avons montré que des molécules faiblement liées de RbSr peuvent être formées à l’aide d’un STIRAP en partant de paires d’atomes isolées et confinées dans un isolant de Mott. Nous avons ensuite étudié leur stabilisation vers le niveau le plus profond de l’état fondamental de la molécule à l’aide d’un second STIRAP. Enfin, nous avons étudié des méthodes se déroulant uniquement dans l’état électronique fondamental. La formation est induite par l’utilisation d’une impulsion à dérive de fréquence induisant un passage adiabatique ou à l’aide d’une impulsion-pi. En plus, nous avons découvert que cette méthode formation peut être reliée à une résonance de Feshbach dans la représentation habillée par les photons, que nous avons appelée Résonance de Feshbach auto-induité assistée par Laser (LASIFR en anglais). Nous montrons qu’elles sont un outil prometteur et puissant pour le contrôle des propriétés de mélange de gaz d’atomes ultra-froids, comme par exemple la longueur de diffusion.

We propose a new type of Feshbach resonance occurring when two different ultracold atoms in their ground state undergo an s-wave collision in the presence of a continuous-wave laser light. The atoms collide in the dissociation continuum of the molecular electronic ground state which is coupled by the light to a rovibrational level of the same electronic ground state: we name this a Laser-Assisted Self-Induced Feshbach Resonance (LASIFR). This mechanism, valid for all polar molecules, is analyzed on the example of ultracold 87Rb and 84Sr atoms, for which the laser frequency falls in the THz range. The control of the LASIFR with the laser frequency and intensity allows for a strong increase of the pair probability density at short distances, which tremendously increases the number of atoms pairs transfered toward the absolute ground state level by STImulated Rapid Adiabatic Passage (STIRAP). The LASIFR results in the observation of a standard Fano profile in the pump transition of the STIRAP process, and is also promising for the optical control of the interspecies scattering length without atom losses.

Ultracold paramagnetic and polar diatomic molecules are among the promising systems for quantum simulation of lattice-spin models. Unfortunately, their experimental observation is still challenging. Based on our recent ab initio calculations, we analyze the feasibility of all-optical schemes for the formation of ultracold Rb-87 Sr-84 bosonic molecules. A first possibility is photoassociation followed by spontaneous emission. The photoassociation rate coefficients toward electronic states converging to the Rb-87(5s( 2)S(1/2)) + Sr-84(5s5p P-3(0,1,2)) asymptotes are particularly small for vibrational levels close to the asymptote. The creation of molecules would be more interesting by using deeply bound levels which preferentially relax to the v '' = 0 level of the ground state. On the other hand, the photoassociation rate coefficients toward electronic states correlated to the Rb(5p P-2(1/2,3/2)) + Sr (5s(2) S-1(0)) are significant for levels close to the asymptote. The spontaneous emission thus creates weakly bound molecules in a single vibrational level. A second option relies on stimulated Raman adiabatic passage implemented in a tight optical trap. It efficiently creates weakly bound ground-state molecules in a well-defined level, thus providing a promising alternative to magnetic Feshbach resonances for further population transfer toward the absolute ground state of the RbSr molecule.

Cryptochromes and photolyases are flavoproteins that may undergo ultrafast charge separation upon electronic excitation of their flavin cofactors. Charge separation involves chains of three or four tryptophan residues depending on the protein of interest. The molecular mechanisms of these processes are not completely clear. In the present work we investigate the relevance of quantum effects like the occurrence of nuclear tunneling and of coherences upon charge transfer in Arabidopsis thaliana cryptochromes. The possible breakdown of the Condon approximation is also investigated. We have devised a simulation protocol based on the realization of molecular dynamics simulations on diabatic potential energy surfaces defined at the hybrid constrained density functional theory/molecular mechanics level. The outcomes of the simulations are analyzed through various dedicated kinetics schemes related to the Marcus theory that account for the aforementioned quantum effects. MD simulations also provide a basic material to define realistic model Hamiltonians for subsequent quantum dissipative dynamics. To carry out quantum simulations, we have implemented an algorithm based on the Hierarchical Equations of Motion. With this new tool in hand we have been able to model the electron transfer chain considering either two- or three-state models. Kinetic models and quantum simulations converge to the conclusion that quantum effects have a significant impact on the rate of charge separation. Nuclear tunneling involving atoms of the tryptophan redox cofactors as well as of the environment (protein atoms and water molecules) is significant. On the other hand non-Condon effects are negligible in most simulations. Taken together, the results of the present work provide new insights into the molecular mechanisms controlling charge separation in this family of flavoproteins.