Optical Shielding of Destructive Chemical Reactions between Ultracold Ground-State NaRb Molecules.

We propose a method to suppress the chemical reactions between ultracold bosonic ground-state ^{23}Na^{87}Rb molecules based on optical shielding. By applying a laser with a frequency blue-detuned from the transition between the lowest rovibrational level of the electronic ground state X^{1}Σ^{+}(v_{X}=0,j_{X}=0), and the long-lived excited level b^{3}Π_{0}(v_{b}=0,j_{b}=1), the long-range dipole-dipole interaction between the colliding molecules can be engineered, leading to a dramatic suppression of reactive and photoinduced inelastic collisions, for both linear and circular laser polarizations. We demonstrate that the spontaneous emission from b^{3}Π_{0}(v_{b}=0,j_{b}=1) does not deteriorate the shielding process. This opens the possibility for a strong increase of the lifetime of cold molecule traps and for an efficient evaporative cooling. We also anticipate that the proposed mechanism is valid for alkali-metal diatomics with sufficiently large dipole-dipole interactions.

Direct observation of bimolecular reactions of ultracold KRb molecules.

Femtochemistry techniques have been instrumental in accessing the short time scales necessary to probe transient intermediates in chemical reactions. In this study, we took the contrasting approach of prolonging the lifetime of an intermediate by preparing reactant molecules in their lowest rovibronic quantum state at ultralow temperatures, thereby markedly 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 (KRb) molecules at a temperature of 500 nanokelvin, we directly observed reactants, intermediates, and products of the reaction 40K87Rb + 40K87Rb → K2Rb2* → K2 + Rb2 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.

Rotational (de)-excitation of cyclic and linear C3H2 by collision with He.

Among the closed-shell hydrocarbons, the carbenes c- and l-C3H2 are the lightest ones to display a permanent electric dipole moment and be detectable by rotational spectroscopy. The cyclic form, cyclopropenylidene, is ubiquitous in the InterStellar Matter (ISM) of the Milky Way and external galaxies. As such, it serves as a marker to help in characterizing the physical conditions of the ISM. The linear form, propadienylidene, is less abundant. In order to get access to their absolute and relative abundances, it is essential to understand their collisional excitation/quenching schemes. We compute here a precise ab initio potential energy surface for the interaction of c- and l-C3H2 with helium, by means of a CCSD(T)-F12a formalism and a fit onto relevant spherical harmonics functions. We conduct quantum dynamical scattering in order to get precise cross sections using a coupled-channel approach for solving the nuclear motion. We average sections to have rates for rotational quenching from 5 to 150 K. We show that these new rates are vastly different, up to more than an order of magnitude, from the older rates presented in the literature, computed with angular momentum algebra only. We expect large differences in the astrophysical analyses of C3H2, including the chemical history of those ubiquitous carbenes.

Rotationally inelastic collisions of H2+ ions with He buffer gas: Computing cross sections and rates.

We present quantum calculations for the inelastic collisions between H2+ molecules, in rotationally excited internal states, and He atoms. This work is motivated by the possibility of experiments in which the molecular ions are stored and translationally cooled in an ion trap and a He buffer gas is added for deactivation of the internal rotational population, in particular at low (cryogenic) translational temperatures. We carry out an accurate representation of the forces at play from an ab initio description of the relevant potential energy surface, with the molecular ion in its ground vibrational state, and obtain the cross sections for state-changing rotationally inelastic collisions by solving the coupled channel quantum scattering equations. The presence of hyperfine and fine structure effects in both ortho- and para-H2+ molecules is investigated and compared to the results where such a contribution is disregarded. An analysis of possible propensity rules that may predict the relative probabilities of inelastic events involving rotational state-changing is also carried out, together with the corresponding elastic cross sections from several initial rotational states. Temperature-dependent rotationally inelastic rates are then computed and discussed in terms of relative state-changing collisional efficiency under trap conditions. The results provide the essential input data for modeling different aspects of the experimental setups which can finally produce internally cold molecular ions interacting with a buffer gas.

Desorption Dynamics of Rb2 Molecules Off the Surface of Helium Nanodroplets.

The desorption dynamics of rubidium dimers (Rb2) off the surface of helium nanodroplets induced by laser excitation is studied by employing both nanosecond and femtosecond ion imaging spectroscopy. Similarly to alkali metal atoms, we find that the Rb2 desorption process resembles the dissociation of a diatomic molecule. However, both angular and energy distributions of detected Rb2+ ions appear to be most crucially determined by the Rb2 intramolecular degrees of freedom rather than by those of the Rb2HeN complex. The pump-probe dynamics of Rb2+ is found to be slower than that of Rb+, pointing at a weaker effective guest-host repulsion for excited molecules than for single atoms.

Ultracold Dipolar Molecules Composed of Strongly Magnetic Atoms.

In a combined experimental and theoretical effort, we demonstrate a novel type of dipolar system made of ultracold bosonic dipolar molecules with large magnetic dipole moments. Our dipolar molecules are formed in weakly bound Feshbach molecular states from a sample of strongly magnetic bosonic erbium atoms. We show that the ultracold magnetic molecules can carry very large dipole moments and we demonstrate how to create and characterize them, and how to change their orientation. Finally, we confirm that the relaxation rates of molecules in a quasi-two-dimensional geometry can be reduced by using the anisotropy of the dipole-dipole interaction and that this reduction follows a universal dipolar behavior.

Long-range interactions between polar bialkali ground-state molecules in arbitrary vibrational levels.

We have calculated the isotropic C6 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)Σ(+). We consider the ten species made up of (7)Li, (23)Na, (39)K, (87)Rb, and (133)Cs. Following our previous work [Lepers et al., Phys. Rev. A 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.

Experimental evidence of twin fast metastable H(2(2)S) atoms from dissociation of cold H2 induced by electrons.

We report the direct detection of two metastable H(2^{2}S) atoms coming from the dissociation of a single cold H(2) molecule, in coincidence measurements. The molecular dissociation was induced by electron impact in order to avoid limitations by the selection rules governing radiative transitions. Two detectors, placed close to the collision center, measure the neutral metastable H(2(2)S) through a localized quenching process, which mixes the H(2^{2}S) state with the H(2^{2}P), leading to a Lyman-α detection. Our data show the accomplishment of a coincidence measurement which proves for the first time the existence of the H(2(2)S)-H(2(2)S) dissociation channel.

Resonant states of the H3(­) molecule and its isotopologues D2H­ and H2D­.

Using the ground potential energy surface [Ayouz, M.; etal. J. Chem. Phys. 2010, 132, 194309] of the H3(­) molecule, we have determined the energies and widths of the complex resonant levels of H3(­) located up to 4000 cm(­1) above the dissociation limit H­ + H2(νd = 0,jd = 0). Bound and resonant levels of the H2D­ and D2H­ isotopologues have been also characterized within the same energy range. The method combines the hyperspherical adiabatic approach, slow variable discretization method, and complex absorbing potential. These results represent the first step for modeling the dynamics of the associated diatom­negative ion collision at low energy involving rotational quenching of the diatom and reactive nucleus exchange via the weak tunneling effect through the potential barrier of the potential energy surface.

Potential energy and dipole moment surfaces of HCO- for the search of H- in the interstellar medium.

Potential energy and permanent dipole moment surfaces of the electronic ground state of formyl negative ion HCO(-) are determined for a large number of geometries using the coupled-cluster theory with single and double and perturbative treatment of triple excitations ab initio method with a large basis set. The obtained data are used to construct interpolated surfaces, which are extended analytically to the region of large separations between CO and H(-) with the multipole expansion approach. We have calculated the energy of the lowest rovibrational levels of HCO(-) that should guide the spectroscopic characterization of HCO(-) in laboratory experiments. The study can also help to detect HCO(-) in the cold and dense regions of the interstellar medium where the anion could be formed through the association of abundant CO with still unobserved H(-).

Formation of ultracold Rb2 molecules in the v'' = 0 level of the a(3)Σ+(u) state via blue-detuned photoassociation to the 1(3)Π(g) state.

We report on the observation of blue-detuned photoassociation in Rb(2), in which vibrational levels are energetically above the corresponding excited atomic asymptote. (85)Rb atoms in a MOT were photoassociated at short internuclear distance to levels of the 1(3)Π(g) state at a rate of approximately 5 × 10(4) molecules s(-1). We have observed most of the predicted vibrational levels for all four spin-orbit components; 0(+)(g), 0(-)(g), 1(g), and 2(g), including levels of the 0(+)(g) outer well. These molecules decay to the metastable a(3)Σ(+)(u) state, some preferentially to the v'' = 0 level, as we have observed for photoassociation to the v' = 8 level of the 1(g) component.

Deeply bound cold caesium molecules formed after 0(-)(g) resonant coupling.

Translationally cold caesium molecules are created by photoassociation below the 6s + 6p(1/2) excited state and selectively detected by resonance enhanced two photon ionization (RE2PI). A series of excited vibrational levels belonging to the 0(-)(g) symmetry is identified. The regular progression of the vibrational spacings and of the rotational constants of the 0(-)(g) (6s + 6p(1/2)) levels is strongly altered in two energy domains. These deviations are interpreted in terms of resonant coupling with deeply bound energy levels of two upper 0(-)(g) states dissociating into the 6s + 6p(3/2) and 6s + 5d(3/2) asymptotes. A theoretical model is proposed to explain the coupling and a quantum defect analysis of the perturbed level position is performed. Moreover, the resonant coupling changes dramatically the spontaneous decay products of the photoexcited molecules, strongly enhancing the decay into deeply bound levels of the a(3)Σ(+)(u) triplet state and of the X(1)Σ(+)(g) ground state. These results may be relevant when conceiving population transferring schemes in cold molecule systems.

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.

Formation of ultracold metastable RbCs molecules by short-range photoassociation.

Ultracold metastable RbCs molecules are observed in a double species magneto-optical trap through photoassociation near the Rb(5S(1/2)) + Cs(6P(3/2)) dissociation limit followed by radiative stabilization. The molecules are formed in their lowest triplet electronic state and are detected by resonance enhanced two-photon ionization through the previously unobserved (3)(3)Π â† a (3)Σ(+) band. The large rotational structure of the observed photoassociation lines is assigned to the lowest vibrational levels of the 0(+) or 0(-) excited states correlated to the Rb(5P(1/2)) + Cs(6S(1/2)) dissociation limit. This demonstrates the possibility of inducing direct photoassociation in heteronuclear alkali-metal molecules at a short internuclear distance, as pointed out earlier [J. Deiglmayr et al., Phys. Rev. Lett., 2008, 101, 13304].

Proposal for a laser control of vibrational cooling in Na(2) using resonance coalescence.

With a specific choice of laser parameters resulting in a so-called exceptional point (EP) in the wavelength-intensity parameter plane, it is possible to produce the coalescence of two Floquet resonances describing the photodissociation of the Na(2) molecule, which is one of the candidates for the formation of samples of translationally cold molecules. By appropriately tuning laser parameters along a contour encircling the exceptional point, the resonances exchange their quantum nature. Thus a laser-controlled transfer of the probability density from one field-free vibrational level to another is achieved through adiabatic transport involving these resonances. We propose an efficient scenario for vibrational cooling of Na(2) referring to cascade transfers involving multiple EPs and predicted to be robust up to a 78% rate against laser-induced dissociation.

Potential energy and dipole moment surfaces of H(3) (-) molecule.

A new potential energy surface for the electronic ground state of the simplest triatomic anion H(3) (-) is determined for a large number of geometries. Its accuracy is improved at short and large distances compared to previous studies. The permanent dipole moment surface of the state is also computed for the first time. Nine vibrational levels of H(3) (-) and 14 levels of D(3) (-) are obtained, bound by at most approximately 70 and approximately 126 cm(-1), respectively. These results should guide the spectroscopic search of the H(3) (-) ion in cold gases (below 100K) of molecular hydrogen in the presence of H(-) ions.

Reinvestigation of the Rb2 (2)3Pi(g)-a 3Sigma(u)+ band on helium nanodroplets.

It is well known that alkali-metal molecules are preferentially observed in the weak van der Waals-bound high spin states by helium droplet isolation spectroscopy. In [F. R. Brühl et al., J. Chem. Phys. 115, 10275 (2001)] the Rb(2) (2)(3)Pi(g)-a (3)Sigma(u)(+) band on He droplets was investigated by laser-induced fluorescence and dispersed emission spectroscopy. At that time no information on the magnitude of spin-orbit coupling was available for the (2)(3)Pi(g) state which connects to the atomic 5s+4d asymptote and it was neglected. In this work we reinvestigate the observed spectra. The dispersed emission spectra, which resulted from free molecules, are consistent with state-of-the-art nonrelativistic potential energy surfaces and effective spin-orbit coupling matrix elements obtained from resonance-enhanced multiphoton ionization spectroscopy of cold Rb dimers [J. Lozeille et al., Eur. Phys. J. D 39, 261 (2006)]. Having validated the theoretical description of the free molecule state, we use the laser-induced fluorescence spectrum to discuss the influence of the He droplet on the excitation band.

Formation of ultracold dipolar molecules in the lowest vibrational levels by photoassociation.

We recently reported the formation of ultracold LiCs molecules in the rovibrational ground state X1sigma+, v" = 0,J" = 0 (J. Deiglmayr et al., Phys. Rev. Lett., 2008, 101, 133004). Here we discuss details of the experimental setup and present a thorough analysis of the photoassociation step including the photoassociation line shape. We predict the distribution of produced ground state molecules using accurate potential energy curves combined with an ab initio dipole transition moment and compare this prediction with experimental ionization spectra. Additionally we improve the value of the dissociation energy for the X1sigma+ state by high resolution spectroscopy of the vibrational ground state.

Formation of ultracold polar molecules in the rovibrational ground state.

Ultracold LiCs molecules in the absolute ground state X1Sigma+, v'' = 0, J'' = 0 are formed via a single photoassociation step starting from laser-cooled atoms. The selective production of v'' = 0, J'' = 2 molecules with a 50-fold higher rate is also demonstrated. The rotational and vibrational state of the ground state molecules is determined in a setup combining depletion spectroscopy with resonant-enhanced multiphoton ionization time-of-flight spectroscopy. Using the determined production rate of up to 5 x 10(3) molecules/s, we describe a simple scheme which can provide large samples of externally and internally cold dipolar molecules.

Calculation of accurate permanent dipole moments of the lowest 1,3Sigma+ states of heteronuclear alkali dimers using extended basis sets.

Obtaining ultracold samples of dipolar molecules is a current challenge which requires an accurate knowledge of their electronic properties to guide the ongoing experiments. In this paper, we systematically investigate the ground state and the lowest triplet state of mixed alkali dimers (involving Li, Na, K, Rb, Cs) using a standard quantum chemistry approach based on pseudopotentials for atomic core representation, Gaussian basis sets, and effective terms for core polarization effects. We emphasize on the convergence of the results for permanent dipole moments regarding the size of the Gaussian basis set, and we discuss their predicted accuracy by comparing to other theoretical calculations or available experimental values. We also revisit the difficulty to compare computed potential curves among published papers, due to the differences in the modelization of core-core interaction.