We theoretically explore photoassociation by Adiabatic Passage of two colliding cold ^{85}Rb atoms in an atomic trap to form an ultracold Rb_2 molecule. We consider the incoherent thermal nature of the scattering process in a trap and show that coherent manipulations of the atomic ensemble, such as adiabatic passage, are feasible if performed within the coherence time window dictated by the temperature, which is relatively long for cold atoms. We show that a sequence of ~2*10^7 pulses of moderate intensities, each lasting ~750 ns, can photoassociate a large fraction of the atomic ensemble at temperature of 100 microkelvin and density of 10^{11} atoms/cm^3. Use of multiple pulse sequences makes it possible to populate the ground vibrational state. Employing spontaneous decay from a selected excited state, one can accumulate the molecules in a narrow distribution of vibrational states in the ground electronic potential. Alternatively, by removing the created molecules from the beam path between pulse sets, one can create a low-density ensemble of molecules in their ground ro-vibrational state.
We have produced ultracold heteronuclear YbRb$^*$ molecules in a combined magneto-optical trap by photoassociation. The formation of electronically excited molecules close to the dissociation limit was observed by trap loss spectroscopy in mixtures of $^{87}$Rb with $^{174}$Yb and $^{176}$Yb. The molecules could be prepared in a series of vibrational levels with resolved rotational structure, allowing for an experimental determination of the long-range potential in the electronically excited state.
The influence of a tight isotropic harmonic trap on photoassociation of two ultracold alkali atoms forming a homonuclear diatomic is investigated using realistic atomic interaction potentials. Confinement of the initial atom pair due to the trap leads to a uniform strong enhancement of the photoassociation rate to most, but also to a strongly suppressed rate for some final states. Thus tighter traps do not necessarily enhance the photoassociation rate. A further massive enhancement of the rate is found for strong interatomic interaction potentials. The details of this interaction play a minor …
Ultracold molecules offer a broad variety of applications, ranging from metrology to quantum computing. However, forming "real" ultracold molecules, {\it i.e.} in deeply bound levels, is a very difficult proposition. Here, we show how photoassociation in the vicinity of a Feshbach resonance enhance molecular formation rates by several orders of magnitude. We illustrate this effect in heteronuclear systems, and find giant rate coefficients even in deeply bound levels. We also give a simple analytical expression for the photoassociation rates, and discuss future applications of the Feshbach Opti…
The creation of ultracold molecules is currently limited to diatomic species. In this letter we present a theoretical description of the photoassociation of ultracold atoms and molecules to create ultracold excited triatomic molecules, thus being a novel example of light-assisted ultracold chemical reaction. The calculation of the photoassociation rate of ultracold Cs atoms with ultracold Cs$_2$ molecules in their rovibrational ground state is reported, based on the solution of the quantum dynamics involving the atom-molecule long-range interactions, and assuming a model potential for the shor…
Photoassociation of ultracold atoms is shown to lead to alignment of the product molecules along the excitation laser polarization axis. We theoretically investigate pulsed photoassociation of $^{87}Rb$ atoms into a specific weakly-bound level of the a $^3Σ_u^+$ metastable electronic state and find both stationary and time-dependent field-free alignment. Although a transform-limited pulse yields significant alignment, a frequency-chirped pulse dramatically enhances the molecular formation rate at the cost of a slight decrease in the alignment. Employing multiple pulses synchronized with the vi…
This theoretical paper investigates the formation of ground state molecules from ultracold cesium atoms in a two-color scheme. Following previous work on photoassociation with chirped picosecond pulses [Luc-Koenig et al., Phys. Rev. A {\bf 70}, 033414 (2004)], we investigate stabilization by a second (dump) pulse. By appropriately choosing the dump pulse parameters and time delay with respect to the photoassociation pulse, we show that a large number of deeply bound molecules are created in the ground triplet state. We discuss (i) broad-bandwidth dump pulses which maximize the probability to f…
Two-color photoassociation of ground state $^6$Li$^{87}$Rb molecules via the $\mathrm{B}^1Π$ electronic state using short pulses near a magnetic Feshbach resonance is studied theoretically. A near-resonant magnetic field is applied to mix the hyperfine singlet and triplet components of the initial wave function and enhance the photoassociation rate, before the population is transferred to the ground state by a second pulse. We show that an increase of up to three orders of magnitude in the absolute number of molecules produced is attainable for deeply bound vibrational levels. This technique c…
We report on two-photon photoassociation (PA) spectroscopy of ultracold heteronuclear LiRb molecules. This is used to determine the binding energies of the loosely bound levels of the electronic ground singlet and the lowest triplet states of LiRb. We observe strong two-photon PA lines with power broadened line widths greater than 20 GHz at relatively low laser intensity of 30 W/cm$^{2}$. The implication of this observation on direct atom to molecule conversion using stimulated Raman adiabatic passage (STIRAP) is discussed and the prospect for electronic ground state molecule production is the…
We analyze coherent two-color photoassociation of a Bose-Einstein condensate, focusing on stimulated Raman adiabatic passage (STIRAP) in free-bound-bound transitions from atoms to molecules. This problem is of particular interest since STIRAP is predicted to be necessarily absent in the nondegenerate case [Javanainen and Mackie, Phys. Rev. A 58, R789 (1998)]. However, Bose-stimulation enhances the free-bound dipole matrix element for an atomic condensate, and photoassociative STIRAP turns out to be a viable mechanism for converting an atomic condensate to a molecular condensate with near-unit …
We explore the feasibility of optically forming long-range tetratomic and larger polyatomic molecules in their ground electronic state from ultracold pairs of polar molecules aligned by external fields. Depending on the relative orientation of the interacting diatomic molecules, we find that a tetratomic can be formed either as a weakly bound complex in a very extended halo state or as a pure long-range molecule composed of collinear or nearly-collinear diatomic molecules. The latter is a novel type of tetratomic molecule comprised of two diatomic molecules bound at long intermolecular range a…
We develop the theory for the Adiabatic Raman Photoassociation (ARPA) of ultracold atoms to form ultracold molecules in the presence of scattering resonances. Based on a computational method in which we replace the continuum with a discrete set of "effective modes", we show that the existence of resonances greatly aids in the formation of deeply bound molecular states. We illustrate our general theory by computationally studying the formation of $^{85}$Rb$_2$ molecules from pairs of colliding ultracold $^{85}$Rb atoms. The single-event transfer yield is shown to have a near-unity value for wid…
The formation of ultracold molecules via stimulated emission followed by a radiative deexcitation cascade in the presence of a static electric field is investigated. By analyzing the corresponding cross sections, we demonstrate the possibility to populate the lowest rotational excitations via photoassociation. The modification of the radiative cascade due to the electric field leads to narrow rotational state distributions in the vibrational ground state. External fields might therefore represent an additional valuable tool towards the ultimate goal of quantum state preparation of molecules.
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 …
Quantum degenerate molecules represent a new paradigm for fundamental studies and practical applications. Association of already quantum degenerate atoms into molecules provides a crucial shortcut around the difficulty of cooling molecules to ultracold temperatures. Whereas association can be induced with either laser or magnetic fields, photoassociation requires impractical laser intensity to overcome poor overlap between the atom pair and molecular wavefunctions, and experiments are currently restricted to magnetoassociation. Here we model realistic production of a quantum degenerate gas of …
In recent experiments on ultracold matter, molecules have been produced from ultracold atoms by photoassociation, Feshbach resonances, and three-body recombination. The created molecules are translationally cold, but vibrationally highly excited. This will eventually lead them to be lost from the trap due to collisions. We propose shaped laser pulses to transfer these highly excited molecules to their ground vibrational level. Optimal control theory is employed to find the light field that will carry out this task with minimum intensity. We present results for the sodium dimer. The final targe…
We present a new mechanism contributing to the detection of photoassociated long-range Rydberg molecules via pulsed-field ionization: ionic products, created by the decay of a long-range Rydberg molecule, modify the excitation spectrum of surrounding ground-state atoms and facilitate the excitation of further atoms into Rydberg states by the photoassociation light. Such an ion-mediated excitation mechanism has been previously called "Coulomb anti-blockade". Pulsed-field ionisation typically doesn't discriminate between the ionization of a long-range Rydberg molecule and an isolated Rydberg ato…
We propose a single-site addressing implementation based on the sub-wavelength localization via adiabatic passage (SLAP) technique. We consider a sample of ultracold neutral atoms loaded into a two-dimensional optical lattice with one atom per site. Each atom is modeled by a three-level Λ-system in interaction with a pump and a Stokes laser pulse. Using a pump field with a node in its spatial profile, the atoms at all sites are transferred from one ground state of the system to the other via stimulated Raman adiabatic passage, except the one at the position of the node that remains in the init…
We theoretically investigate Raman photoassociation of a degenerate Bose-Fermi mixture of atoms and the subsequent prospect for anomalous (Cooper) pairing between atoms and molecules. Stable fermionic molecules are created via free-bound-bound stimulated Raman adiabatic passage which, in contrast to purely bosonic systems, can occur in spite of collisions. With the leftover atomic condensate to enhance intrafermion interactions, the superfluid transition to atom-molecule Cooper pairs occurs at a temperature that is roughly an order of magnitude below what is currently feasible.
We have produced large samples of ultracold $^{88}$Sr$_2$ molecules in the electronic ground state in an optical lattice. The molecules are bound by 0.05 cm$^{-1}$ and are stable for several milliseconds. The fast, all-optical method of molecule creation via intercombination line photoassociation relies on a near-unity Franck-Condon factor. The detection uses a weakly bound vibrational level corresponding to a very large dimer. This is the first of two steps needed to create Sr$_2$ in the absolute ground quantum state. Lattice-trapped Sr$_2$ is of interest to frequency metrology and ultracold …
A semiclassical, four-level model of a nanosecond, chirped pulse interacting with all optically accessible hyperfine states in the ultracold Rb atom is analyzed aiming at population inversion within $5S_{1/2}$ electronic state. The nature of two-photon adiabatic passage performed by such a single pulse having a bandwidth smaller than the hyperfine splitting of $5S_{1/2}$ state is investigated in the framework of the dressed state picture. It is shown that two dressed states are involved in the adiabatic dynamics of population inversion. The excited state manifold appeared to play an important …
We present a theoretical analysis of optical pathways for formation of cold Ca($^1$S)Na$^+$($^1$S) molecular ions via an intermediate state. The formation schemes are based on ab initio potential energy curves and transition dipole moments calculated using effective-core-potential methods of quantum chemistry. In the proposed approach, starting from a mixture of cold trapped Ca$^+$ ions immersed into an ultracold gas of Na atoms, (NaCa)$^+$ molecular ions are photoassociated in the excited E$^{1}Σ^+$ electronic state and allowed to spontaneously decay either to the ground electronic state or a…
Ultracold ground-state molecules can be formed from ultracold atoms via photoassociation followed by a spontaneous emission process. Typically, the molecular products are distributed over a range of final states. Here, we propose to use an optical cavity with high cooperativity to selectively enhance the population of a pre-determined final state by controlling the spontaneous emission. During this process, a photon will be emitted into the cavity mode. Detection of this photon heralds a single reaction. We discuss the efficiency and the dynamics of cavity-assisted molecule formation in the fr…
We study coherent photoassociation, phenomena analogous to coherent optical transients in few-level systems, which may take place in photoassociation of an atomic Bose-Einstein condensate but not in a nondegenerate gas. We develop a second-quantized Hamiltonian to describe photoassociation, and apply the Hamiltonian both in the momentum representation and in the position representation (field theory). Solution of the two-mode problem including only one mode each for the atomic and molecular condensates displays analogs of Rabi oscillations and rapid adiabatic passage. A classical version of th…
We propose a new approach to excite ion-pair states of ultracold dimers. The central idea is a two-step process where first long-range Rydberg molecules are formed by photoassociation, which are then driven by stimulated emission towards the ion-pair state, a process bearing features of a photo-induced harpooning reaction. We assess the feasibility of this approach through a detailed experimental and theoretical study on a specific system, p-wave-scattering dominated long-range Rydberg molecules in caesium, and discuss potential applications for the study of strongly correlated plasmas consist…
Spatial adiabatic passage processes for ultracold atoms trapped in tunnel-coupled cylindrically symmetric concentric potentials are investigated. Specifically, we discuss the matter-wave analogue of the rapid adiabatic passage (RAP) technique for a high fidelity and robust loading of a single atom into a harmonic ring potential from a harmonic trap, and for its transport between two concentric rings. We also consider a system of three concentric rings and investigate the transport of a single atom between the innermost and the outermost rings making use of the matter-wave analogue of the stimu…
We investigate the stimulated Raman adiabatic passage in two-color photoassociation for a atom-molecule Bose-Einstein condensate. By applying two time-varying Guassian laser pulses that fulfill generalized two-photon resonance condition, we obtain highly efficient atom-molecule conversion. The efficiency depends on the free-bound detuning and the delay time between the two pulses. By adjusting the parameters optimally, we achieve 92% conversion efficiency.
We study dynamics of a two-color photoassociation of atoms into diatomic molecules via nonlinear Stimulated Raman adiabatic passage (STIRAP) process. This system has a famous counterpart in (linear) quantum mechanics, and been discussed recently in the context of generalizing quantum adiabatic theorem to nonlinear systems. Here we use another approach to study adiabaticity and stability in the system: we apply methods of classical Hamiltonian dynamics. We found nonlinear dynamical instabilities, cases of complete integrability, and improved conditions of adiabaticity.
Photoassociation (PA) is a powerful technique to synthesize molecules directly and continuously from cold and ultracold atoms into deeply bound molecular states. In freespace, however, PA efficiency is constrained by the number of spontaneous decay channels linking the initial excited molecular state to a sea of final (meta)stable rovibronic levels. Here, we propose a novel scheme based on molecules strongly coupled to a guided photonic mode in a photonic crystal waveguide that turns PA into a powerful tool for near deterministic formation of ultracold molecules in their ground rovibrational l…
Chemical reactions at ultracold temperatures are expected to be dominated by quantum mechanical effects. Although progress towards ultracold chemistry has been made through atomic photoassociation, Feshbach resonances and bimolecular collisions, these approaches have been limited by imperfect quantum state selectivity. In particular, attaining complete control of the ground or excited continuum quantum states has remained a challenge. Here we achieve this control using photodissociation, an approach that encodes a wealth of information in the angular distribution of outgoing fragments. By phot…
We examine the passage of ultracold two-level atoms through two separated laser fields for the nonresonant case. We show that implications of the atomic quantized motion change dramatically the behavior of the interference fringes compared to the semiclassical description of this optical Ramsey interferometer. Using two-channel recurrence relations we are able to express the double-laser scattering amplitudes by means of the single-laser ones and to give explicit analytical results. When considering slower and slower atoms, the transmission probability of the system changes considerably from a…
We study ultracold long-range collisions of heteronuclear alkali-metal dimers with a reservoir gas of alkali-metal Rydberg atoms in a two-photon laser excitation scheme. In a low density regime where molecules remain outside the Rydberg orbits of the reservoir atoms, we show that the two-photon photoassociation (PA) of the atom-molecule pair into a long-range bound trimer state is efficient over a broad range of atomic Rydberg channels. As a case study, we obtain the PA lineshapes for the formation of trimers composed of KRb molecules in the rovibrational ground state and excited Rb atoms in t…
We report efficient all-optical creation of an ultracold gas of alkaline-earth-metal dimers, $^{88}\rm{Sr}_2$, in their absolute ground state. Starting with weakly bound singlet molecules formed by narrow-line photoassociation in an optical lattice, followed by stimulated Raman adiabatic passage (STIRAP) via a singlet-dominant channel in the $(1)0_u^+$ excited potential, we prepare pure samples of more than 5500 molecules in $X^1Σ_g^+(v=0,J=0)$. We observe two-body collisional loss rates close to the universal limit for both the least bound and most bound vibrational states in $X^1Σ_g^+$. We d…
The Fano effect or Fano resonance with a characteristically asymmetric line shape originates from quantum interference between direct and indirect transition pathways in continuum-bound coupled systems, and is a ubiquitous phenomenon in atomic, molecular, nuclear and solid-state physics. In optical nanoscale structures, the Fano effect has wide-ranging applications that include optical filtering, sensing, all-optical switching, quantum interferometry and nonlinear optics, and this opens new avenues for photonic devices. The emergent area of ultracold atomic and molecular gases presents an idea…
Collective two-color photoassociation of a freely-interacting 87Rb Bose-Einstein condensate is theoretically examined, focusing on stimulated Raman adiabatic passage (STIRAP) from an atomic to a stable molecular condensate. In particular, Drummond et al. [Phys. Rev. A 65, 063619 (2002); cond-mat/0110578] have predicted that particle-particle interactions can limit the efficiency of collective atom-molecule STIRAP, and that optimizing the laser parameters can partially overcome this limitation. We suggest that the molecular conversion efficiency can be further improved by treating the initial c…
We propose a class of schemes for robust population transfer between quantum states that utilize trains of coherent pulses and represent a generalized adiabatic passage via a wave packet. We study piecewise Stimulated Raman Adiabatic Passage with pulse-to-pulse amplitude variation, and piecewise chirped Raman passage with pulse-to-pulse phase variation, implemented with an optical frequency comb. In the context of production of ultracold ground-state molecules, we show that with almost no knowledge of the excited potential, robust high-efficiency transfer is possible
We survey results on the creation of heteronuclear Fermi molecules by tuning a degenerate Bose-Fermi mixture into the neighborhood of an association resonance, either photoassociation or Feshbach, as well as the subsequent prospects for Cooper-like pairing between atoms and molecules. In the simplest case of only one molecular state, corresponding to either a Feshbach resonance or one-color photoassociation, the system displays Rabi oscillations and rapid adiabatic passage between a Bose-Fermi mixture of atoms and fermionic molecules. For two-color photoassociation, the system admits stimulate…
We propose schemes of controlled-Z and controlled-NOT gates with ultracold neutral atoms based on deterministic phase accumulation during double adiabatic passage of the Stark-tuned Förster resonance of Rydberg states. The effect of deterministic phase accumulation during double adiabatic passage in a two-level quantum system has been analyzed in detail. Adiabatic rapid passage using nonlinearly chirped pulses with rectangle intensity profile has been discussed. Nonlinear time dependence of the energy detuning from the Förster resonance is used to achieve a high fidelity of population transfer…
We suggest and analyze a novel technique for efficient and robust creation of dense ultracold molecular ensembles in their ground rovibrational state. In our approach a molecule is brought to the ground state through a series of intermediate vibrational states via a {\em multistate chainwise Stimulated Raman Adiabatic Passage} (c-STIRAP) technique. We study the influence of the intermediate states decay on the transfer process and suggest an approach that minimizes the population of these states, resulting in a maximal transfer efficiency. As an example, we analyze the formation of $^{87}$Rb$_…
We report the observation and analysis of the $3\,^3Π_Ω$ double-minimum electronic excited state of $^{39}$K$^{85}$Rb. The spin-orbit components ($0^{+}, 0^{-}, 1$ and 2) of this state are investigated based on potentials developed from the available \emph{ab initio} potential curves. We have assigned the vibrational levels $v'=2-11$ of the $3\,^3Π_{1,2}$ potentials and $v'=2-12$ of the $3\,^3Π_{0^{+/-}}$ potential. We compare our experimental observations of the $3\,^3Π_Ω$ state with predictions based on theoretical potentials. The observations are based on resonance enhanced multiphoton ioni…
We present an overview of our recent investigations of long-range interactions in an ultracold Cs Rydberg gas. These interactions are studied by high-resolution photoassociation spectroscopy, using excitation close to one-photon transitions into $n$p$_{3/2}$ Rydberg states with pulsed and continuous-wave ultraviolet laser radiation, and lead to the formation of long-range Cs$_2$ molecules. We observe two types of molecular resonances. The first type originates from the correlated excitation of two atoms into Rydberg-atom-pair states interacting at long range via multipole-multipole interaction…
We report on the creation of bosonic NaCs molecules in their absolute rovibrational ground state via stimulated Raman adiabatic passage. We create ultracold gases with up to 22,000 dipolar NaCs molecules at a temperature of 300(50) nK and a peak density of $1.0(4) \times 10^{12}$ cm$^{-3}$. We demonstrate comprehensive quantum state control by preparing the molecules in a specific electronic, vibrational, rotational, and hyperfine state. Employing the tunability and strength of the permanent electric dipole moment of NaCs, we induce dipole moments of up to 2.6 D. Dipolar systems of NaCs molecu…
We propose a method of constructing cold atom analogs of the spintronic device known as the Datta-Das transistor (DDT), which despite its seminal conceptual role in spintronics, has never been successfully realized with electrons. We propose two alternative schemes for an atomic DDT, both of which are based on the experimental setup for tripod stimulated Raman adiabatic passage. Both setups involve atomic beams incident on a series of laser fields mimicking the relativistic spin orbit coupling for electrons that is the operating mechanism of the DDT.
We produce ultracold dense trapped samples of 87Rb133Cs molecules in their rovibrational ground state, with full nuclear hyperfine state control, by stimulated Raman adiabatic passage (STIRAP) with efficiencies of 90%. We observe the onset of hyperfine-changing collisions when the magnetic field is ramped so that the molecules are no longer in the hyperfine ground state. A strong quadratic shift of the transition frequencies as a function of applied electric field shows the strongly dipolar character of the RbCs ground-state molecule. Our results open up the prospect of realizing stable bosoni…
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 ran…
The precision of the photoassociation spectroscopy of Yb dimer in degenerate gases is enough to improve the constraints on the new short-range gravity-like forces if the theoretical knowledge of the Born-Oppenheimer interatomic potential and non-Born-Oppenheimer interactions is refined [M. Borkowski et al. Sci. Rep. A {\bf 9}, 14807 (2019)]. The ground-state interaction potential of ytterbium dimer is investigated at the eXact 2-component core-correlated CCSD(T) level of {\it ab initio} theory in the complete basis set limit with extensive augmentation by diffuse functions. For the small basis…
High-fidelity entangled Bell states are of great interest in quantum physics. Entanglement of ultracold neutral atoms in two spatially separated optical dipole traps is promising for implementation of quantum computing and quantum simulation and for investigation of Bell states of material objects. We propose a new method to entangle two atoms via long-range Rydberg-Rydberg interaction. Alternatively to previous approaches, based on Rydberg blockade, we consider radiofrequency-assisted Stark-tuned Förster resonances in Rb Rydberg atoms. To reduce the sensitivity of the fidelity of Bell states …
We have performed high resolution photoassociation spectroscopy of rubidium ultra long-range Rydberg molecules in the vicinity of the 25$P$ state. Due to the hyperfine interaction in the ground state perturber atom, the emerging mixed singlet-triplet potentials contain contributions from both hyperfine states. We show that this can be used to induce remote spin-flips in the perturber atom upon excitation of a Rydberg molecule. When furthermore the spin-orbit splitting of the Rydberg state is comparable to the hyperfine splitting in the ground state, the orbital angular momentum of the Rydberg …
We report on the creation of an ultracold dipolar gas of fermionic $^{23}$Na$^{40}$K molecules in their absolute rovibrational and hyperfine ground state. Starting from weakly bound Feshbach molecules, we demonstrate hyperfine resolved two-photon transfer into the singlet ${\rm X}^1Σ^+ |v{=}0,J{=}0\rangle$ ground state, coherently bridging a binding energy difference of 0.65 eV via stimulated rapid adiabatic passage. The spin-polarized, nearly quantum degenerate molecular gas displays a lifetime longer than 2.5 s, highlighting NaK's stability against two-body chemical reactions. A homogeneous …
