arXiv subjects

Olivier Dulieu

Publications and source records attributed to Olivier Dulieu.

At least 19 recordsLinked to original sources

arXiv2026

Rotational laser spectroscopy of the $X^1Σ_g^+\rightarrow B^1Π_u$ transition of $\text{Rb}_2$ molecule in a supersonic beam: As good as it gets

High-resolution laser spectroscopy of the $^{85}\mathrm{Rb}_2$, $^{85}\mathrm{Rb}^{87}\mathrm{Rb}$, and $^{87}\mathrm{Rb}_2$ isotopologues has been performed in a supersonic molecular beam using a continuous-wave (cw) tunable diode laser. A total of 958 rovibronic transitions were recorded up to $7~\mathrm{cm}^{-1}$ below the vibrational band heads of the $X^1Σ_g^+(v''=0)\rightarrow B^1Π_u(v'=1,2)$ and $X^1Σ_g^+(v''=1)\rightarrow B^1Π_u(v'=1)$ bands, with a spectral resolution of $3.3\times10^{-4}$~cm$^{-1}$. Although restricted to the $v'=1$ and $v'=2$ vibrational levels of the excited $B^1Π_u$ state, the measurements extend previous work by Amiot and Vergès [Chemical Physics Letters 274, 91 (1997)] through substantially higher resolution and dense low-$J'$ rotational data for all three isotopologues. A global least-squares analysis combining the new and published data, yields improved Dunham coefficients for the excited $B^1Π_u$ state, significantly refines rotational and rovibrational coupling constants. In addition, the $Λ$-doubling constants of $B^1Π_u$ state were determined for the three isotopologues.

physics.atom-ph↗

arXiv2026

Demonstration of deuterium's enhanced sensitivity to symmetry violations governed by the Standard-Model Extension

We have performed hyperfine spectroscopy of two transitions in ground-state deuterium and searched for violations of CPT and Lorentz symmetry that would manifest as sidereal variations of the observed transition frequencies. Several nonrelativistic proton coefficients of the Standard-Model Extension framework have been addressed. The spin-independent coefficients with momentum power k=2,4 are constrained for the first time. Bounds on spin-dependent coefficients are improved by exploiting a sensitivity enhancement originating from the relative momenta of the nucleons in the deuteron. The best previous constraints by hydrogen maser measurements are surpassed by 4 and 14 orders of magnitude for coefficients with k=2 and 4, respectively.

hep-ex↗

arXiv2026

Quantum study of ultracold atom-ion excitation exchange

The quantum dynamics of ultracold collisions between rubidium atoms and excited metastable strontium ions is treated in the laboratory frame, enlightening the importance of the coupling between internal angular momenta of the particles and their mutual rotation. The study reveals a subtle competition between electronic excitation exchange and fine structure quenching, with no charge exchange, which is found to be very sensitive to the details of ion-atom interactions. The rate constant for electronic excitation exchange is found in agreement with the experimental results of Ben-Shlomi \textit{et al.} (Phys. Rev. A \textbf{102}, 031301(R) (2020)), while the rate for fine structure quenching is predicted to strongly depend on the initial polarization of the reactants.

physics.atom-ph↗

arXiv2026

An Alternate Pathway for H$_2$ Formation in the Early Universe: A physical process to account for the presence and coevolution of the luminous galaxies and supermassive black holes at the high redshifts

Molecular hydrogen (H$_2$) and hydrogen deuteride (HD) are key coolants in primordial gas and regulate the formation of the first stars and proto-galaxies. Recent results from the James Webb Space Telescope provide striking insights into galaxies detected at high redshifts, which are found to be significantly more abundant and luminous than expected from galaxy formation models, thus suggesting a gap in our understanding of the early Universe. Standard pathways for H$_2$ formation in the early Universe proceed through the H$^-$ and H$_2^+$ intermediates, both of which are strongly suppressed at high redshift by the cosmic microwave background. We propose an additional pathway for H2 and HD formation that could be active as early as the end of the epoch of recombination and could enable the formation of the first stars earlier than the current prediction at redshift z ~ 30 - 20. The proposed pathway relies on the manifestation of Jahn-Teller dynamical coupling between electronic states of H$_3^+$. This coupling induces transient three-body recombination in H$^+$, H and H, and charge exchange within the charged atom-dimer complex that directly creates ground-state H$_2$ (and HD), bypassing the fragile intermediates that limit the standard primordial pathways. Our analysis shows that this mechanism could occur under the thermodynamic conditions of the post-recombination epoch, also suggesting that it might be playing a role in the active galactic nuclei feedback processes, regulating the formation rates of the first stars and the accretion rates of the first black holes. Though the global impact on galaxy formation and black-hole growth is not yet determined and will require quantitative assessment in future modeling, the mechanism offers an additional chemical route for H$_2$ and HD formation, with substantial cosmological relevance for primordial chemistry and early structure formation.

astro-ph.GA↗

arXiv2026

Two-photon-assisted collisions in ultracold gases of polar molecules II : Optical shielding of ultracold polar molecular collisions

We theoretically investigate the collisions between ultracold polar molecules in the presence of two lasers ensuring a Raman resonant transition on individual molecules to suppress photon scattering, taking the example of bosonic $^{23}$Na$^{39}$K molecules. By varying laser detunings and intensities, we enable a repulsive long-range interaction potential between molecules. After solving a set of coupled Schrödinger equations with the Hamiltonian written in the basis of laser-dressed states of the molecule pair at infinite distance, we identify quasi-resonant conditions under which elastic collisions are favored over inelastic and reactive ones, by a factor of about 2, thus demonstrating a promising pathway for efficient two-photon optical shielding of ultracold molecular collisions. The results are analyzed in terms of scattering length of the colliding laser-dressed molecules, which exhibit prominent resonances assigned to the interaction of the entrance channel with other specific channels, consistent with the existence of a quasi-bound level of the long-range molecular pair induced by the lasers.

cond-mat.quant-gas↗

arXiv2026

Hyperfine-resolved optical spectroscopy of ultracold $^{87}$Rb$^{133}$Cs molecules: the $\mathrm{b}\,^3Π_0$ metastable state

Using an ultracold gas of $^{87}$Rb$^{133}$Cs molecules, we perform hyperfine-resolved spectroscopy of transitions from the vibronic ground state to the lowest rovibrational states of the electronic state $\mathrm{b}\,^3Π_0$, as a function of magnetic field. These transitions are spin forbidden, resulting in narrow linewidths, and feature near-diagonal Franck-Condon factors. We develop a model of the hyperfine and Zeeman structure that includes coupling between the $0^+$ and $0^-$ components of $\mathrm{b}\,^3Π_0$. We fit the spectra to obtain rotational and hyperfine coupling constants. We measure transition dipole moments associated with specific transitions by directly observing Rabi oscillations as a function of a resonant laser pulse duration. Using resonant $π$ pulses, we prepare molecules in the electronically excited state and directly measure the spontaneous emission rate.

physics.atom-ph↗

arXiv2025

Optical formation of ultracold NaK$_2$ ground state molecules

We study the rovibronic transitions in NaK$_2$ between its electronic ground state $1^2A'$ and its second excited state $3^2A'$, to identify possible pathways for the creation of ultracold ground-state triatomic molecules. Our methodology relies on the computation of potential energy surfaces and transition dipole moment surfaces for the relevant electronic states using ab initio methods. Rovibrational energy levels and wave functions are determined using the discrete variable representation approach. A double-well structure of the potential energy surface is identified for both states, and the related transition strengths between the rovibrational levels are derived. Our calculations show that the formation of ultracold ground-state NaK$_2$ molecules is expected when starting from an excited electronic state of NaK$_2$, which can be created by photoassociation of NaK and K observed by optical means by Cao et al. (Phys. Rev. Lett. 2024, 132, 093403).

cond-mat.quant-gas↗

arXiv2025

Two-photon-assisted collisions in ultracold gases of polar molecules

We present a theoretical formalism to treat the ultracold dynamics of a pair of colliding polar molecules submitted to two laser fields. We express the dressed Hamiltonian including the dipole-dipole interaction of the colliding molecular pair, both in their ground and electronic excited states, as well as their interaction with the two laser fields. We apply adiabatic elimination of the electronic excited state to reduce the size of the dressed-state basis in which the dressed Hamiltoninan is expressed. In an application, we investigate the feasibility of two-photon collisional shielding between two \NaK molecules, which could be favored by the Raman resonance condition suppressing unwanted spontaneous emission and photon scattering. We demonstrate the influence of the laser Rabi frequencies on the dynamics through the computation of elastic, inelastic, and reactive collision rates.

cond-mat.quant-gas↗

arXiv2025

Ionization Energy of Rb$_2$ by electric field-ionization of molecular Rydberg states

We report the measurement of the ionization energy of the $^{85}\text{Rb}_2$ molecule through resonantly enhanced 2-photon ionization in a supersonic beam. The first photon excites the $X^1Σ_g^+ (v_X = 0)\rightarrow B^1Π_u (v_B = 2)$ transition, while the second photon wavenumber is scanned over the 16720 cm$^{-1}$-16750 cm$^{-1}$ range, thus yielding a structured spectrum of Rb$_2^+$ ions extracted by an electric field and recorded by mass spectrometry. We modeled the onset of the ionization signal as a function of the electric field strength between $18 V/cm$ and $180 V/cm$, leading to the Rb$_2$ ionization energy $E_i = 31497.3 \pm 0.6 $cm$^{-1}$, and to the dissociation energy of the Rb$_2^+$ ground state $D_0 = 6158.2 \pm 0.6$ cm$^{-1}$. Our measured value $E_i$ is found to be $149.3$ cm$^{-1}$ larger than the one reported in the experiment by Bellos et al. [Phys. Rev. A 87, 012508 (2013)]. Our value of $D_0$ agrees with our theoretical determination using a quantum chemistry approach. Using a simple theoretical model, we assign unevenly spaced structures of the ionization spectrum to molecular Rydberg levels belonging to several series that converge to the lowest vibrational levels of Rb$_2^+$.

physics.atom-ph↗

arXiv2025

Ultracold Interactions between Ions and Polar Molecules

We propose a platform for observing and controlling the interactions between atomic ions and a quantum gas of polar molecules in the ultracold regime. This approach is based on the combination of several recently developed methods in two so-far complementary research domains: ion-atom collisions and studies of ultracold polar molecules. In contrast to collisions between ions and ground-state atoms, which are dominated by losses due to three-body recombination (TBR) already at densities far below those typical for quantum degenerate ensembles, our proposal makes use of polar molecules, their rich level structure, and sensitivity to electric fields to design effective interaction potentials where ion-neutral TBR losses and molecule-molecule losses due to sticky collisions could be strongly suppressed. This may open a broad range of applications including precise control of collisional properties in molecular ensembles using ions, quantum simulations, and cold quantum chemistry between polyatomic molecules.

physics.atom-ph↗

arXiv2025

Formation of ultracold triatomic molecules by electric microwave association

A theoretical model is proposed for the formation of ultracold ground-state triatomic molecules in weakly bound energy levels. The process is driven by the electric component of a microwave field, which induces the association of an ultracold atom colliding with an ultracold diatomic molecule. This model is exemplified using $^{39}$K atoms and $^{23}$Na$^{39}$K molecules, both in their ground states, a scenario of experimental relevance. The model assumes that the dynamics of the association are dominated by the long-range van der Waals interaction between $^{39}$K and $^{23}$Na$^{39}$K. The electric microwave association mechanism relies on the intrinsic electric dipole moment of $^{23}$Na$^{39}$K, which drives transitions between its lowest rotational levels ( $j$=0 and $j$=1). The energies of the uppermost triatomic energy levels are computed by numerically solving coupled Schrödinger equations using the Mapped Fourier Grid Hamiltonian method. Measurable association rates are derived within the framework of a perturbative approach. This method of electric microwave association provides an alternative to atom-molecule association via magnetic Feshbach resonances for forming ultracold, deeply bound triatomic molecules, and is applicable to a wide range of polar diatomic molecules.

physics.atom-ph↗

arXiv2024

Ultracold charged atom-dimer collisions: state-selective charge exchange and three-body recombination

Based on an accurate determination of the potential energy surfaces of Rb$_3^+$ correlated to its first asymptotic limit Rb$^+$$+$Rb($5s$)$+$Rb($5s$), we identify the presence of intersections of a pair of singlet and triplet surfaces over all interparticle distances, leading to Jahn-Teller couplings. We elaborate scenarios for charge exchange between ultracold charged atom-dimer complex (Rb$+$Rb$_2^+$ or Rb$^+$$+$Rb$_2$), predicting a strong selectivity on the preparation of the initial state of the dimer. We also demonstrate that the JT couplings must drive the three-body recombination (TBR) of Rb$^+$, Rb, and Rb at ultracold energies. Using the current analysis, we provide a consistent picture of the TBR experiments performed in ion-atom hybrid Rb samples \cite{dieterle2020inelastic,harter2012single}. We also demonstrate the presence of JT coupling as a general phenomenon in the singly-charged homonuclear alkali triatomic systems.

physics.atom-ph↗

arXiv2024

Competing excitation quenching and charge exchange in ultracold Li-Ba$^+$ collisions

Hybrid atom-ion systems are a rich and powerful platform for studying chemical reactions, as they feature both excellent control over the electronic state preparation and readout as well as a versatile tunability over the scattering energy, ranging from the few-partial wave regime to the quantum regime. In this work, we make use of these excellent control knobs, and present a joint experimental and theoretical study of the collisions of a single $^{138}$Ba$^+$ ion prepared in the $5d\,^2D_{3/2,5/2}$ metastable states with a ground state $^6$Li gas near quantum degeneracy. We show that in contrast to previously reported atom-ion mixtures, several non-radiative processes, including charge exchange, excitation exchange and quenching, compete with each other due to the inherent complexity of the ion-atom molecular structure. We present a full quantum model based on high-level electronic structure calculations involving spin-orbit couplings. Results are in excellent agreement with observations, highlighting the strong coupling between the internal angular momenta and the mechanical rotation of the colliding pair, which is relevant in any other hybrid system composed of an alkali-metal atom and an alkaline-earth ion.

quant-ph↗

arXiv2023

Charge transfer of polyatomic molecules in ion-atom hybrid traps: Stereodynamics in the millikelvin regime

Rate constants for the charge transfer reaction between N${}_{2}$H${}^{+}$ and Rb in the mK regime are measured in an ion-atom hybrid trap and are found to be lower than the Langevin capture limit. Multireference ab initio computation of the potential energy surfaces involved in the reaction reveals that the low-temperature charge transfer is hindered by short-range features highly dependent on the collision angle and is promoted by a deformation of the molecular frame. The present study highlights the importance of polyatomic effects and of stereodynamics in cold molecular ion-neutral collisions.

physics.atom-ph↗

arXiv2023

Two-photon optical shielding of collisions between ultracold polar molecules

We propose a method to engineer repulsive long-range interactions between ultracold ground-state molecules using optical fields, thus preventing short-range collisional losses. It maps the microwave coupling recently used for collisional shielding onto a two-photon transition, and takes advantage of optical control techniques. In contrast to one-photon optical shielding [Phys. Rev. Lett. 125, 153202 (2020)], this scheme avoids heating of the molecular gas due to photon scattering. The proposed protocol, exemplified for 23Na39K, should be applicable to a large class of polar diatomic molecules.

quant-ph↗

arXiv2023

Modeling photoassociative spectra of ultracold NaK+K

A model for photoassociation of ultracold atoms and molecules is presented, and applied to the case of $^{39}$K and $^{23}$Na$^{39}$K bosonic particles. The model relies on the assumption that photoaossociation is dominated by long-range atom-molecule interactions, well outside the chemical bond region. The frequency of the photoassociation laser is chosen close to a bound-bound rovibronic transition from the $X^1Σ^+$ ground state toward the metastable $b^3Π$ lowest excited state of $^{23}$Na$^{39}$K, allowing to neglect any other excitation which could hinder the photoassociation detection. The energy level structure of the long-range $^{39}$K$\cdots$$^{23}$Na$^{39}$K excited super-dimer is computed in the space-fixed frame by solving coupled-channel equations, involving the coupling between the $^{23}$Na$^{39}$K internal rotation with the mechanical rotation of the super-dimer complex. A quite rich structure is obtained, and the corresponding photoassociation rates are presented. Other possible photossociation transitions are discussed in the context of the proposed model.

physics.chem-ph↗

arXiv2023

FitAik: a package to calculate least-square fitted atomic transitions probabilities. Application to the Er+ lanthanide ion

We present a new method implemented in our new package \textit{FitAik}, to perform least-squares fitting of calculated and experimental atomic transition probabilities, by using the mono-electronic transition integrals $\langle n\ell |r| n'\ell' \rangle$ (with $r$ the electronic radial coordinate) as adjustable quantities. \textit{FitAik} is interfaced to the Cowan suite of codes, for which it automatically writes input files and reads output files. We illustrate our procedure with the example of Er$^{+}$ ion, for which the agreement between calculated and experimental Einstein coefficients is found to be very good. The source code of \emph{FitAik} can be found on GitLab, and the calculated Einstein coefficients are stored in our new database CaDDiACs. They are also used to calculate the dynamic dipole polarizability of Er$^+$.

physics.atom-ph↗

arXiv2022

Ion loss events in a cold Rb-Ca$^+$ hybrid trap: photodissociation, black-body radiation and non-radiative charge exchange

We theoretically investigate the collisional dynamics of laser-cooled $^{87}$Rb ground-state atoms and $^{40}$Ca$^+$ ground-state ions in the context of the hybrid trap experiment of Ref. [Phys. Rev. Lett. 107, 243202 (2011)], leading to ion losses. Cold $^{87}$Rb$^{40}$Ca$^+$ ground-state molecular ions are created by radiative association, and we demonstrate that they are protected against photodissociation by black-body radiation and by the $^{40}$Ca$^+$ cooling laser at 397~nm. This study yields an interpretation of the direct observation of $^{87}$Rb$^{40}$Ca$^+$ ions in the experiment, in contrast to other hybrid trap experiments using other species. Based on novel molecular data for the spin-orbit interaction, we also confirm that the non-radiative charge-exchange is the dominant loss process for Ca$^+$ and obtain rates in agreement with experimental observations and a previous calculation.

physics.chem-ph↗