arXiv subjects

Olivier Dulieu

Publications and source records attributed to Olivier Dulieu.

At least 73 records · Page 4Linked to original sources

arXiv2013

Ion-neutral chemistry at ultralow energies: Dynamics of reactive collisions between laser-cooled Ca^+ ions and Rb atoms in an ion-atom hybrid trap

Cold chemical reactions between laser-cooled Ca^+ ions and Rb atoms were studied in an ion-atom hybrid trap. Reaction rate constants were determined in the range of collision energies /k_B = 20 mK-20 K. The lowest energies were achieved in experiments using single localized Ca^+ ions. Product branching ratios were studied using resonant-excitation mass spectrometry. The dynamics of the reactive processes in this system (non-radiative and radiative charge transfer as well as radiative association leading to the formation of CaRb^+ molecular ions) have been analyzed using high-level quantum-chemical calculations of the potential energy curves of CaRb^+ and quantum-scattering calculations for the radiative channels. For the present low-energy scattering experiments, it is shown that the energy dependence of the reaction rate constants is governed by long-range interactions in line with the classical Langevin model, but their magnitude is determined by short-range non-adiabatic and radiative couplings which only weakly depend on the asymptotic energy. The quantum character of the collisions is predicted to manifest itself in the occurrence of narrow shape resonances at well-defined collision energies. The present results highlight both universal and system-specific phenomena in cold ion-neutral reactive collisions.

physics.atom-ph↗

arXiv2013

Light-Assisted Cold Chemical Reactions of Barium Ions with Rubidium Atoms

Light-assisted reactive collisions between laser-cooled Ba+ ions and Rb atoms were studied in an ion-atom hybrid trap. The reaction rate was found to strongly depend on the electronic state of the reaction partners with the largest rate constant (7(2) x 10^-11 cm^3 s^-1) obtained for the excited Ba+(6s)+Rb(5p) reaction channel. Similar to the previously studied Ca+ + Rb system, charge transfer and radiative association were found to be the dominant reactive processes. The generation of molecular ions by radiative association could directly be observed by their sympathetic cooling into a Coulomb crystal. Potential energy curves up to the Ba+(6s)+Rb(5p) asymptote and reactive-scattering cross sections for the radiative processes were calculated. The theoretical rate constant obtained for the lowest reaction channel Ba+(6s)+Rb(5s) is compatible with the experimental estimates obtained thus far.

physics.atom-ph↗

arXiv2012

Long-range interactions in the ozone molecule: spectroscopic and dynamical points of view

Using the multipolar expansion of the electrostatic energy, we have characterized the asymptotic interactions between an oxygen atom O$(^3P)$ and an oxygen molecule O$_2(^3Σ_g^-)$, both in their electronic ground state. We have calculated the interaction energy induced by the permanent electric quadrupoles of O and O$_2$ and the van der Waals energy. On one hand we determined the 27 electronic potential energy surfaces including spin-orbit connected to the O$(^3P)$ + O$_2(^3Σ_g^-)$ dissociation limit of the O--O$_2$ complex. On the other hand we computed the potential energy curves characterizing the interaction between O$(^3P)$ and a O$_2(^3Σ_g^-)$ molecule in its lowest vibrational level and in a low rotational level. Such curves are found adiabatic to a good approximation, namely they are only weakly coupled to each other. These results represent a first step for modeling the spectroscopy of ozone bound levels close to the dissociation limit, as well as the low energy collisions between O and O$_2$ thus complementing the knowledge relevant for the ozone formation mechanism.

physics.chem-ph↗

arXiv2011

Light-assisted ion-neutral reactive processes in the cold regime: radiative molecule formation vs. charge exchange

We present a combined experimental and theoretical study of cold reactive collisions between laser-cooled Ca+ ions and Rb atoms in an ion-atom hybrid trap. We observe rich chemical dynamics which are interpreted in terms of non-adiabatic and radiative charge exchange as well as radiative molecule formation using high-level electronic structure calculations. We study the role of light-assisted processes and show that the efficiency of the dominant chemical pathways is considerably enhanced in excited reaction channels. Our results illustrate the importance of radiative and non-radiative processes for the cold chemistry occurring in ion-atom hybrid traps.

physics.atom-ph↗

arXiv2011

Photoassociative creation of ultracold heteronuclear 6Li40K* molecules

We investigate the formation of weakly bound, electronically excited, heteronuclear 6Li40K* molecules by single-photon photoassociation in a magneto-optical trap. We performed trap loss spectroscopy within a range of 325 GHz below the Li(2S_(1/2))+K(4P_(3/2)) and Li(2S_(1/2))+K(4P_(1/2)) asymptotic states and observed more than 60 resonances, which we identify as rovibrational levels of 7 of 8 attractive long-range molecular potentials. The long-range dispersion coefficients and rotational constants are derived. We find large molecule formation rates of up to ~3.5x10^7s^(-1), which are shown to be comparable to those for homonuclear 40K_2*. Using a theoretical model we infer decay rates to the deeply bound electronic ground-state vibrational level X^1Σ^+(v'=3) of ~5x10^4s^(-1). Our results pave the way for the production of ultracold bosonic ground-state 6Li40K molecules which exhibit a large intrinsic permanent electric dipole moment.

physics.atom-ph↗

arXiv2011

Long-range interactions between ultracold atoms and molecules including atomic spin-orbit

We investigate theoretically the long-range electrostatic interactions between a ground-state homonuclear alkali-metal dimer and an excited alkali-metal atom taking into account its fine-structure. The interaction involves the combination of first-order quadrupole-quadrupole and second-order dipole-dipole effects. Depending on the considered species, the atomic spin-orbit may be comparable to the atom-molecule electrostatic energy and to the dimer rotational structure. Here we extend our general description in the framework of the second-order degenerate perturbation theory [M. Lepers and O. Dulieu, Eur. Phys. J. D, 2011] to various regimes induced by the magnitude of the atomic spin-orbit. A complex dynamics of the atom-molecule may take place at large distances, which may have consequences for the search for an universal model of ultracold inelastic collisions as proposed for instance in [Z. Idziaszek and P. S. Julienne, Phys. Rev. Lett. \textbf{104}, 113202 (2010)].

physics.chem-ph↗

arXiv2011

Molecular spectroscopy for ground-state transfer of ultracold RbCs molecules

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 (A1Σ+ - b3Π0) 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 X1Σ+ 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.

physics.atom-ph↗

arXiv2011

Formation of H$_3^-$ by radiative association of H$_2$ and H$^-$ in the interstellar medium

We develop the theory of radiative association of an atom and a diatomic molecule within a close-coupling framework. We apply it to the formation of H$_3^-$ after the low energy collision (below 0.5 eV) of H$_2$ with H$^-$. Using recently obtained potential energy and permanent dipole moment surfaces of H$_3^-$, we calculate the lowest rovibrational levels of the H$_3^-$ electronic ground state, and the cross section for the formation of H$_3^-$ by radiative association between H$^-$ and ortho- and para-H$_2$. We discuss the possibility for the H$_3^-$ ion to be formed and observed in the cold and dense interstellar medium in an environment with a high ionization rate. Such an observation would be a probe for the presence of H$^-$ in the interstellar medium.

physics.atom-ph↗

arXiv2011

Structure of the Alkali-metal-atom-Strontium molecular ions: towards photoassociation and formation of cold molecular ions

The potential energy curves, permanent and transition dipole moments, and the static dipolar polarizability, of molecular ions composed of one alkali-metal atom and a Strontium ion are determined with a quantum chemistry approach. The molecular ions are treated as effective two-electron systems and are treated using effective core potentials including core polarization, large gaussian basis sets, and full configuration interaction. In the perspective of upcoming experiments aiming at merging cold atom and cold ion traps, possible paths for radiative charge exchange, photoassociation of a cold Lithium or Rubidium atom and a Strontium ion are discussed, as well as the formation of stable molecular ions.

quant-ph↗

arXiv2011

Optimal trapping wavelengths of Cs$_2$ molecules in an optical lattice

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.

quant-ph↗

arXiv2011

Ultracold atom-dimer long-range interactions beyond the $1/R^{n}$ expansion

We investigate theoretically the combination of first-order quadrupole-quadrupole and second-order dipole-dipole effects on the long-range electrostatic interactions between a ground-state homonuclear alkali-metal dimer and an excited alkali-metal atom. As the electrostatic energy is comparable to the dimer rotational structure, we develop a general description of the long-range interactions which allows for couplings between the dimer rotational levels. The resulting adiabatic potential energy curves, which exhibit avoided crossings, cannot be expanded on the usual $1/R^{n}$ series. We study in details the breakdown of this approximation in the particular case Cs$_{2}+$Cs. Our results are found promising in the prospect of accomplishing the photoassociation of ultracold trimers.

quant-ph↗

arXiv2010

Laser control of complete vibrational transfer in Na$_2$ using resonance coalescence

With a specific choice of laser parameters resulting into a so-called exceptional point in the wavelength-intensity plane, it is possible to produce the coalescence of two Floquet resonances describing the photodissociation of the molecule Na$_2$, which is one of the candidates for molecular cooling. Appropriately tuning laser parameters, following a contour around the exceptional point, the resonances exchange their labels. This represents a laser control of the vibrational transfer from one field-free state to another, through an adiabatic transport involving these resonances. The proportion of undissociated molecules at the end of the pulse is checked through Floquet adiabatic theory. A vibrational cooling scenario can be proposed based on a complete vibrational transfer which is predicted, with only 20 percent of molecules undergoing dissociation.

quant-ph↗

arXiv2010

Triplet-singlet conversion in ultracold Cs$_2$ and production of ground state molecules

We propose a process to convert ultracold metastable Cs$_2$ molecules in their lowest triplet state into (singlet) ground state molecules in their lowest vibrational levels. Molecules are first pumped into an excited triplet state, and the triplet-singlet conversion is facilitated by a two-step spontaneous decay through the coupled $A^{1}Σ_{u}^{+} \sim b ^{3}Π_{u}$ states. Using spectroscopic data and accurate quantum chemistry calculations for Cs$_2$ potential curves and transition dipole moments, we show that this process has a high rate and competes favorably with the single-photon decay back to the lowest triplet state. In addition, we demonstrate that this conversion process represents a loss channel for vibrational cooling of metastable triplet molecules, preventing an efficient optical pumping cycle down to low vibrational levels.

quant-ph↗

arXiv2010

The ground state of the polar alkali-Strontium molecules: potential energy curve and permanent dipole moment

In this study, we investigate the structure of the polar alkali-Strontium diatomic molecules as possible candidates for the realization of samples of new species of ultracold polar molecules. Using a quantum chemistry approach based on Effective Core Potentials and Core Polarization Potentials, we model these systems as effective three valence electron systems, allowing for calculation of electronic properties with Full Configuration Interaction. The potential curve and the permanent dipole moment of the $^2Σ^+$ ground state are determined as functions of the internuclear distances for LiSr, NaSr, KSr, RbSr, and CsSr molecules. These molecules are found to exhibit a significant permanent dipole moment, though smaller than those of the alkali-Rb molecules.

physics.atm-clus↗

arXiv2010

Photoionization spectroscopy of excited states of cold cesium dimers

Photoionization spectroscopy of cold cesium dimers obtained by photoassociation of cold atoms in a magneto-optical trap is reported here. In particular, we report on the observation and on the spectroscopic analysis of all the excited states that have actually been used for efficient detection of cold molecules stabilized in the triplet a^3Sigma_u^+ ground state. They are: the (1)^3Sigma_g^+ state connected to the 6s+6p asymptote, the (2)^3Sigma_g^+ and (2)^3Pi_g states connected to the 6s+5d asymptote and finally the (3)^3Sigma_g^+ state connected to the 6s + 7s asymptote. The detection through these states spans a wide range of laser energies, from 8000 to 16500 cm-1, obtained with different laser dyes and techniques. Information on the initial distribution of cold molecules among the different vibrational levels of the a^3Sigma_u^+ ground state is also provided. This spectroscopic knowledge is important when conceiving schemes for quantum manipulation, population transfer and optical detection of cold cesium molecules.

physics.chem-ph↗

arXiv2009

Formation and interactions of cold and ultracold molecules: new challenges for interdisciplinary physics

Progress on researches in the field of molecules at cold and ultracold temperatures is reported in this review. It covers extensively the experimental methods to produce, detect and characterize cold and ultracold molecules including association of ultracold atoms, deceleration by external fields and kinematic cooling. Confinement of molecules in different kinds of traps is also discussed. The basic theoretical issues related to the knowledge of the molecular structure, the atom-molecule and molecule-molecule mutual interactions, and to their possible manipulation and control with external fields, are reviewed. A short discussion on the broad area of applications completes the review.

quant-ph↗

arXiv2009

Optimization of Generalized Multichannel Quantum Defect reference functions for Feshbach resonance characterization

This work stresses the importance of the choice of the set of reference functions in the Generalized Multichannel Quantum Defect Theory to analyze the location and the width of Feshbach resonance occurring in collisional cross-sections. This is illustrated on the photoassociation of cold rubidium atom pairs, which is also modeled using the Mapped Fourier Grid Hamiltonian method combined with an optical potential. The specificity of the present example lies in a high density of quasi-bound states (closed channel) interacting with a dissociation continuum (open channel). We demonstrate that the optimization of the reference functions leads to quantum defects with a weak energy dependence across the relevant energy threshold. The main result of our paper is that the agreement between the both theoretical approaches is achieved only if optimized reference functions are used.

quant-ph↗

arXiv2009

Core repulsion effects in alkali trimers

The present paper is related to a talk presented during the Symposium on Coherent Control and Ultracold Chemistry held during the Sixth Congress of the International Society for Theoretical Chemical Physics (ISTCP-VI, July 2008). The talk was entitled "Electronic structure properties of alkali dimers and trimers. Prospects for alignment of ultracold molecules". Here we report on the electrostatic repulsion forces of the ionic cores at short separation, involved when the potential energy surfaces of alkali trimers are calculated with a quantum chemistry approach based on effective large-core potentials for ionic core description. We demonstrate that such forces in the triatomic molecule can be obtained as the sum of three pairwise terms. We illustrate our results on the lowest electronic states of Cs$_3$, which are computed for the first time within a full configuration interaction based on a large Gaussian basis set. As a preliminary section, we also propose a brief introduction about the importance of alkali trimer systems in the context of cold and ultracold molecules.

physics.atm-clus↗