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Polar quantum gases represent promising platforms for studying many-body physics and strongly correlated systems with possible applications e.g. in quantum simulation or quantum computation. Due to their large permanent electric dipole moment polar molecules in electric field exhibit strong long-range anisotropic dipole-dipole interactions (DDIs). The creation and trapping of ultracold dipolar diatomic molecules of various species are feasible in many experimental groups nowadays. However long time trapping is still a challenge even in the case of the so called nonreactive molecules which are supposed to be immune against inelastic collisions in their absolute ground state [1] . Various hypothesis have been invoked to explain the possible mechanisms behind the trapping loss, however the check of their pertinence is not trivial since the final products can not be easily detected [2] . To overcome the loss processes we propose the suppression of inelastic collisions between molecules using optical shielding (OS). OS relies on the modification of long-range interactions between ground-state and excited molecules by laser light. The first experimental proof of OS process was demonstrated in case of the collision between identical ultracold alkali-metal atoms [3] .

We calculate the isotope-independent ${\mathrm{Li}}^{+}$-Li potential energy curves for the electronic ground and first excited states. The scattering phase shifts and total scattering cross section for the $^{7}\mathrm{Li}^{+}\text{\ensuremath{-}}^{7}\mathrm{Li}$ collision are calculated, with an emphasis on the ultralow-energy domain down to the $s$-wave regime. The effect of physically motivated alterations on the calculated potential energy curves is used to determine the bound of accuracy of the low-energy scattering parameters for the ion-atom system. It is found that the scattering length for the $A{\phantom{\rule{0.16em}{0ex}}}^{2}{\mathrm{\ensuremath{\Sigma}}}_{u}^{+}$ state, ${a}_{u}=1325{a}_{0}$, is positive and has well-constrained bounds. For the $X{\phantom{\rule{0.16em}{0ex}}}^{2}{\mathrm{\ensuremath{\Sigma}}}_{g}^{+}$ state, the scattering length, ${a}_{g}=20\phantom{\rule{0.16em}{0ex}}465{a}_{0}$, has a large magnitude, as it is sensitive to the restrained change of the potential, due to the presence of a vibrational state in the vicinity of the dissociation limit.

Ultracold atom-ion collisions are an emerging field of research that can ultimately lead to their precise quantum control. In collisions in which the ion is prepared in an excited state, previous studies showed that the dominant reaction pathway was charge exchange. Here, we explored the outcome products and the energy released from a single ultracold collision between a single $^{88}\mathrm{Sr}^{+}$ ion and a single $^{87}\mathrm{Rb}$ atom prepared in excited metastable and ground electronic states, respectively, with control over their relative spins. We found that the ion's long-lived ${D}_{5/2}$ and ${D}_{3/2}$ states quench after roughly three collisions, acquiring immense kinetic energy in the process. By performing single-shot thermometry on the ion after the collision, we identified two dominant reaction pathways: electronic excitation exchange and spin-orbit change. In contrast to previous experiments, we observed no charge-exchange events. These processes are theoretically understood to occur through Landau-Zener avoided crossings leading to the observed reaction pathways. We also found that spin orientation has almost no effect on the reaction pathways, due to strong Coriolis-spin mixing. Our results provide a deeper understanding of ultracold atom-ion inelastic collisions and offer additional quantum control tools for the cold chemistry field.

We study polar alkali-metal dimer scattering in a quasi-one-dimensional geometry for both reactive and nonreactive species. Elastic and reactive rates are computed as a function of the amplitude of a static electric field within a purely long-range model with suitable boundary conditions at shorter range. We describe the diatomic molecules as rigid rotors and results are compared to the fixed-dipole approximation. We show in particular that for molecules with a sufficiently strong induced dipole moment oriented perpendicular to the trap axis, the long-range repulsive interaction leads to the suppression of short-range processes. Such shielding effect occurs for both reactive and nonreactive molecules, preventing two-body reactions as well as losses due to complex-mediated processes [M. Mayle et al., Phys. Rev. A 85, 062712 (2012)] from occurring. The present results demonstrate the possibility to suppress loss rates in current ultracold molecule experiments using one-dimensional confinement.

Femtochemistry techniques have been instrumental in accessing the short time scales necessary to probe transient intermediates in chemical reactions. Here we take the contrasting approach of prolonging the lifetime of an intermediate by preparing reactant molecules in their lowest ro-vibronic quantum state at ultralow temperatures, thereby drastically reducing the number of exit channels accessible upon their mutual collision. Using ionization spectroscopy and velocity-map imaging of a trapped gas of potassium-rubidium molecules at a temperature of 500~nK, we directly observe reactants, intermediates, and products of the reaction $^{40}$K$^{87}$Rb + $^{40}$K$^{87}$Rb $\rightarrow$ K$_2$Rb$^*_2$ $\rightarrow$ K$_2$ + Rb$_2$. Beyond observation of a long-lived energy-rich intermediate complex, this technique opens the door to further studies of quantum-state resolved reaction dynamics in the ultracold regime., Comment: 4 figures in main, 4 figures in SM, 2 table in SM

The dipolar collision between ultracold polar molecules is an important topic both by its own right from the fundamental point of view and for the successful exploration of many-body physics with strong and long-range dipolar interactions. Here, we report the investigation of collisions between ultracold ground-state sodium-rubidium molecules in electric fields with induced electric dipole moments as large as 0.7$\;$D. We observe a step-wise enhancement of losses due to the coupling between different partial waves induced by the increasingly stronger anisotropic dipolar interactions. Varying the temperature of our sample, we find good agreement with theoretical loss rates assuming complex formation as the main loss process. Our results shed new light on the understanding of complex molecular collisions in the presence of strong dipolar interactions and also demonstrate the versatility of modifying molecular interactions with electric fields., 8 pages, 4 figures, PRX in press

We report a detailed molecular spectroscopy study of the lowest excited electronic states of $^{23}\mathrm{Na}\phantom{\rule{0.16em}{0ex}}^{87}\mathrm{Rb}$ for producing ultracold $^{23}\mathrm{Na}\phantom{\rule{0.16em}{0ex}}^{87}\mathrm{Rb}$ molecules in the electronic, rovibrational, and hyperfine ground state. Starting from weakly bound Feshbach molecules, a series of vibrational levels of the $A{\phantom{\rule{0.16em}{0ex}}}^{1}{\mathrm{\ensuremath{\Sigma}}}^{+}\text{\ensuremath{-}}b{\phantom{\rule{0.16em}{0ex}}}^{3}\mathrm{\ensuremath{\Pi}}$ coupled excited states is investigated. After resolving, modeling, and interpreting the hyperfine structure of several lines, we successfully identify a long-lived level resulting from the accidental hyperfine coupling between the ${0}^{+}$ and ${0}^{\ensuremath{-}}$ components of the $b{\phantom{\rule{0.16em}{0ex}}}^{3}\mathrm{\ensuremath{\Pi}}$ state, satisfying all the requirements for the population transfer toward the lowest rovibrational level of the $X{\phantom{\rule{0.16em}{0ex}}}^{1}{\mathrm{\ensuremath{\Sigma}}}^{+}$ state. Using two-photon spectroscopy, its binding energy is measured to be 4977.308(3) ${\mathrm{cm}}^{\ensuremath{-}1}$. We calibrate all the transition strengths carefully and also demonstrate Raman transfer of Feshbach molecules to the absolute ground state.

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The direct photodissociation of trapped ${^{85}\mathrm{Rb}}_{2}^{+}$ (rubidium) molecular ions by the cooling light for the $^{85}\mathrm{Rb}$ magneto-optical trap (MOT) is studied, both experimentally and theoretically. Vibrationally excited ${\mathrm{Rb}}_{2}^{+}$ ions are created by photoionization of ${\mathrm{Rb}}_{2}$ molecules formed photoassociatively in the Rb MOT and are trapped in a modified spherical Paul trap. The decay rate of the trapped ${\mathrm{Rb}}_{2}^{+}$ ion signal in the presence of the MOT cooling light is measured and agreement with our calculated rates for molecular ion photodissociation is observed. The photodissociation mechanism due to the MOT light is expected to be active and therefore universal for all homonuclear diatomic alkali metal molecular ions.

We report on the observation of three RbCs satellite bands in the blue and green ranges of the visible spectrum. Absorption measurements are performed using all-sapphire cell filled with a mixture of Rb and Cs. We compare high resolution absorption spectrum of Rb-Cs vapor mixture with pure Rb and Cs vapor spectra from the literature. After detailed analysis, the new satellite bands of RbCs molecule at 418.3 nm, 468.3, and 527.5 nm are identified. The origin of these bands is discussed by direct comparison with difference potentials derived from quantum chemistry calculations of RbCs potential energy curves. These bands originate from the lower Rydberg states of the RbCs molecule. This study thus provides further insight into photoassociation of lower Rydberg molecular states, approximately between Cs(7s) + Rb(5s) and Cs(6s) + Rb(6p) asymptotes, in ultracold gases.

A new bosonic species of ultracold alkali heteromolecule with a considerable electric dipole moment has been cooled to its vibrational ground state.

We report a high-resolution spectroscopic investigation of the long-range states of the (NaRb)-Na-23-Rb-87 molecule near its Na(3 S-2(1/2))+Rb(5 P-2(3/2)) asymptote. This study was performed with weakly bound ultracold molecules produced via magnetoassociation with an interspecies Feshbach resonance. We observed several regular vibrational series, which are assigned to the five attractive long-range states correlated with this asymptote. The vibrational levels of two of these states have sharp but complex structures due to hyperfine and Zeeman interactions. For the other states we observed significant linewidth broadenings due to strong predissociation caused by spin-orbit couplings with states correlated to the lower Na(3 S-2(1/2))+Rb(5 P-2(1/2)) asymptote. The long-range C-6 van der Waals coefficients extracted from our spectrum are in good agreement with theoretical values.

The direct photodissociation of trapped ^{85}Rb_{2}^{+} (rubidium) molecular ions by the cooling light for the ^{85}Rb magneto-optical trap (MOT) is studied, both experimentally and theoretically. Vibrationally excited Rb_{2}^{+} ions are created by photoionization of Rb_{2} molecules formed photoassociatively in the Rb MOT and are trapped in a modified spherical Paul trap. The decay rate of the trapped Rb_{2}^{+} ion signal in the presence of the MOT cooling light is measured and agreement with our calculated rates for molecular ion photodissociation is observed. The photodissociation mechanism due to the MOT light is expected to be active and therefore universal for all homonuclear diatomic alkali metal molecular ions.

We study, both theoretically and experimentally, the dynamical polarizability of molecules in the rovibrational ground state of . Taking all relevant excited molecular bound states into account, we compute the complex-valued polarizability for wave numbers up to 20 000 . Our calculations are compared to experimental results at ( ) as well as at ( ). Here, we discuss the measurements at . The ultracold Rb2 molecules are trapped in the lowest Bloch band of a 3D optical lattice. Their polarizability is determined by lattice modulation spectroscopy which measures the potential depth for a given light intensity. Moreover, we investigate the decay of molecules in the optical lattice, where lifetimes of more than are observed. In addition, the dynamical polarizability for the state is calculated. We provide simple analytical expressions that reproduce the numerical results for for all vibrational levels of as well as . Precise knowledge of the molecular polarizability is essential for designing experiments with ultracold molecules as lifetimes and lattice depths are key parameters. Specifically the wavelength at is of interest, since here, ultrastable high power lasers are available., publishedVersion

A model for determining the hyperfine structure of the excited electronic states of diatomic bialkali heteronuclear molecules is formulated from the atomic hyperfine interactions, and is applied to the case of bosonic $^{39}$KCs and fermionic $^{40}$KCs molecules. The hyperfine structure of the potential energy curves of the states correlated to the K($4s\,^2S_{1/2}$)+Cs($6p\,^2P_{1/2,3/2}$) dissociation limits is described in terms of different coupling schemes depending on the internuclear distance $R$. These results provide the first step in the calculation of the hyperfine structure of rovibrational levels of these excited molecular states in the perspective of the identification of efficient paths for creating ultracold ground-state KCs molecules., Comment: 12 pages, 15 figures

Efficient laser scheme to create ultracold KRb molecules into their rovibronic ground state using stimulated Raman adiabatic passage was presented and state-of-the-art molecular potentials, spin-orbit couplings, and transition strengths are used to perform the involved calculations.

We computed the long-range interactions between two identical polar bialkali molecules in their rovibronic ground level, for all ten species involving Li, Na, K, Rb and Cs, using accurate quantum chemistry results combined with available spectroscopic data. Huge van der Waals interaction is found for eight species in free space. The competition of the van der Waals interaction with the dipole-dipole interaction induced by an external electric field parallel or perpendicular to the intermolecular axis is investigated by varying the electric field magnitude and the intermolecular distance. Our calculations predict a regime with the mutual orientation of the two molecules but with no preferential direction in the laboratory frame. A mechanism for the stimulated one-photon radiative association of a pair of ultracold polar molecules into ultracold tetramers is proposed, which would open the way towards the optical manipulation of ultracold polyatomic molecules., 9 pages, 5 figures

The present paper aims at finding optimal parameters for trapping of Cs$_2$ molecules in optical lattices, with the perspective of creating a quantum degenerate gas of ground-state molecules. We have calculated dynamic polarizabilities of Cs$_2$ molecules subject to an oscillating electric field, using accurate potential curves and electronic transition dipole moments. We show that for some particular wavelengths of the optical lattice, called "magic wavelengths", the polarizability of the ground-state molecules is equal to the one of a Feshbach molecule. As the creation of the sample of ground-state molecules relies on an adiabatic population transfer from weakly-bound molecules created on a Feshbach resonance, such a coincidence ensures that both the initial and final states are favorably trapped by the lattice light, allowing optimized transfer in agreement with the experimental observation.

We perform one- and two-photon high resolution spectroscopy on ultracold samples of RbCs Feshbach molecules with the aim to identify a suitable route for efficient ground-state transfer in the quantum-gas regime to produce quantum gases of dipolar RbCs ground-state molecules. One-photon loss spectroscopy allows us to probe deeply bound rovibrational levels of the mixed excited (A1{\Sigma}+ - b3{\Pi}0) 0+ molecular states. Two-photon dark state spectroscopy connects the initial Feshbach state to the rovibronic ground state. We determine the binding energy of the lowest rovibrational level |v"=0,J"=0> of the X1{\Sigma}+ ground state to be DX 0 = 3811.5755(16) 1/cm, a 300-fold improvement in accuracy with respect to previous data. We are now in the position to perform stimulated two-photon Raman transfer to the rovibronic ground state., Comment: Submitted to PCCP themed issue: Physics and Chemistry of Cold Molecules

The electrostatic interaction between an excited atom and a diatomic ground state molecule in an arbitrary rovibrational level at large mutual separations is investigated with a general second-order perturbation theory, in the perspective of modeling the photoassociation between cold atoms and molecules. We find that the combination of quadrupole-quadrupole and van der Waals interactions compete with the rotational energy of the dimer, limiting the range of validity of the perturbative approach to distances larger than 100 a.u.. Numerical results are given for the long-range interaction between Cs and Cs$_2$, showing that the photoassociation is probably efficient whatever the Cs$_2$ rotational energy., Comment: 6 figures, 2 tables

Heteronuclear alkali-metal dimers represent the class of molecules of choice for creating samples of ultracold molecules exhibiting an intrinsic large permanent electric dipole moment. Among them, the KCs molecule, with a permanent dipole moment of 1.92 Debye still remains to be observed in ultracold conditions. Based on spectroscopic studies available in the literature completed by accurate quantum chemistry calculations, we propose several optical coherent schemes to create ultracold bosonic and fermionic KCs molecules in their absolute rovibrational ground level, starting from a weakly bound level of their electronic ground state manifold. The processes rely on the existence of convenient electronically excited states allowing an efficient stimulated Raman adiabatic transfer of the level population.

We have calculated the isotropic $C\_6$ coefficients characterizing the long-range van der Waals interaction between two identical heteronuclear alkali-metal diatomic molecules in the same arbitrary vibrational level of their ground electronic state $X^1\Sigma^+$. We consider the ten species made up of $^7$Li, $^{23}$Na, $^{39}$K, $^{87}$Rb and $^{133}$Cs. Following our previous work [M.~Lepers \textit{et.~al.}, Phys.~Rev.~A \textbf{88}, 032709 (2013)] we use the sum-over-state formula inherent to the second-order perturbation theory, composed of the contributions from the transitions within the ground state levels, from the transition between ground-state and excited state levels, and from a crossed term. These calculations involve a combination of experimental and quantum-chemical data for potential energy curves and transition dipole moments. We also investigate the case where the two molecules are in different vibrational levels and we show that the Moelwyn-Hughes approximation is valid provided that it is applied for each of the three contributions to the sum-over-state formula. Our results are particularly relevant in the context of inelastic and reactive collisions between ultracold bialkali molecules, in deeply bound or in Feshbach levels.

The dynamics of ultracold quantum gases composed of atoms or molecules with extremely low translational energy Et/kB << 1 millikelvin is dominated by the long-range mutual interactions between particles. Such studies require a detailed modelling of the atom-molecule or molecule-molecule long-range interactions inside the quantum gas with or without the presence of external fields. This paper focuses on two particular aspects relevant to ultracold chemistry: (i) The calculation of rates for photoassociation of a cold atom and a cold molecule to create ultracold excited trimers, based on the knowledge of the long-range interaction between the two species, showing that such rates are encouraging under the density and temperature conditions of a nearly degenerate quantum gas; (ii) The determination of the long-range interactions between two identical polar bialkali molecules in their rovibronic ground level in the presence of an electric field, showing the possibility for the formation of ultracold polar tetramers by stimulated emission.

The theoretical work presented in this thesis is focused on the formation of ultracold bialcaline molecules and on the control of their external and internal degrees of freedom. This study is motivated by the increasing number of experiments aiming at obtaining a quantum degenerate gas of molecules in their absolute ground state. The formation scheme we worked on is based on the Stimulated Raman Adiabatic Passage (STIRAP) technique operated while molecules are trapped inside an optical lattice.We have determined the parameters of the optical lattice (intensity and wavelength of the laser) that allow for an efficient trapping of the alkali dimers by evaluating the dynamic polarizability of molecules in the presence of an external field. Such calculations require the accurate knowledge of the electronic structure of the molecules. We have identified the so-called ``magic'' wavelength for which all levels populated during the STIRAP sequence have the same polarizability, thus ensuring an optimal transfer. The same approach has also been used to compute the strength of the long-range interaction between polar bialkali molecules needed to evaluate collision rates.The particular case of the RbCs molecule has been investigated. We have selected a radiative transition allowing for an efficient STIRAP scheme yielding molecules in their rovibrational ground state. These works have raised the need for the precise knowledge of the hyperfine structure of the excited electronic molecular state involved in the STIRAP scheme. We have developed an asymptotic model to obtain a first estimate of the hyperfine structure for the potential curves of the lowest excited states of Cs2 and RbCs.; Le travail théorique présenté dans cette thèse concerne la formation de molécules ultra-froides bialcalines et le contrôle de leurs degrés de liberté externes et internes. Cette étude est motivée par les nombreuses expériences en cours visant à l'obtention d'un gaz quantique dégénéré de molécules dans leur état fondamental absolu. Le schéma de formation étudié repose sur le processus de transfert adiabatique stimulé (STIRAP) réalisé en présence d'un potentiel optique de piégeage (réseau optique) des atomes et des molécules.Nous avons déterminé les paramètres du réseau optique (intensité et fréquence du champ laser) qui permettent de piéger efficacement des dimères d'alcalins en évaluant la polarisabilité dynamique acquise par les molécules soumises à un champ externe. Ces calculs reposent en particulier sur la connaissance détaillée de la structure électronique des molécules. Nous avons identifié des plages de longueur d'ondes dites « magiques » où la polarisabilité est la même pour chaque niveau peuplé au cours du transfert adiabatique, permettant ainsi un transfert optimal. Ce formalisme nous a également permis d'obtenir les coefficients Van der Waals de l'interaction à longue portée nécessaires pour étudier les taux de collisions entre molécules.Nous avons réalisé une étude plus détaillée de la molécule RbCs. En étudiant précisément la probabilité de transition de la molécule vers un niveau excité, nous avons proposé un schéma STIRAP pour transférer des molécules de RbCs, initialement dans un niveau vibrationnel excité, vers leur état rovibrationnel fondamental.Ces travaux ont montré l'importance de la connaissance précise de la structure hyperfine de l'état électronique moléculaire excité pour réaliser un gaz dégénéré de molécules dans un état quantique bien défini. Un modèle asymptotique nous a permis d'obtenir une première estimation de la structure hyperfine des courbes d'énergies potentielles des premiers états moléculaires excités des molécules Cs2 et RbCs.