Rovibrational Ground State Research Articles

Dynamics of thermal Casimir-Polder forces on polar molecules

We study the influence of thermal Casimir-Polder forces on the near-surface trapping of cold polar molecules, with emphasis on LiH and YbF near an Au surface at room temperature. We show that for a molecule initially prepared in its electronic and rovibrational ground state, the Casimir-Polder force oscillates with the molecule-wall separation. The non-resonant force contribution and the evanescent part of the resonant force contribution almost exactly cancel at high temperature which results in a saturation of the (attractive) force in this limit. A dynamical calculation reveals how the spatial oscillations die out as thermalisation of the molecule with its environment sets in.

Influence of a Feshbach resonance on the photoassociation of LiCs

We analyze the formation of ultracold 7Li133Cs molecules in the rovibrational ground state through photoassociation into the B1Π state, which has recently been reported (Deiglmayr et al 2008 Phys. Rev. Lett. 101 133004). Absolute rate constants for photoassociation at large detunings from the atomic asymptote are determined and are found to be surprisingly large. The photoassociation process is modeled using a full coupled-channel calculation for the continuum state, taking all relevant hyperfine states into account. The enhancement of the photoassociation rate is found to be caused by an ‘echo’ of the triplet component in the singlet component of the scattering wave function at the inner turning point of the lowest triplet a3Σ+ potential. This perturbation can be ascribed to the existence of a broad Feshbach resonance at low scattering energies. Our results elucidate the important role of couplings in the scattering wave function for the formation of deeply bound ground state molecules via photoassociation.

Collisional and molecular spectroscopy in an ultracold Bose–Bose mixture

The route towards a Bose–Einstein condensate (BEC) of dipolar molecules requires the ability to efficiently associate dimers of different chemical species and transfer them to the stable rovibrational ground state. Here, we report on recent spectroscopic measurements of two weakly bound molecular levels and newly observed narrow d-wave Feshbach resonances. The data are used to improve the collisional model for the Bose–Bose mixture 41K87Rb, one of the most promising candidates to create a molecular dipolar BEC.

Deeply bound ultracold molecules in an optical lattice

We demonstrate efficient transfer of ultracold molecules into a deeply bound rovibrational level of the singlet ground state potential in the presence of an optical lattice. The overall molecule creation efficiency is 25%, and the transfer efficiency to the rovibrational level |v=73,J=2⟩ is above 80%. We find that the molecules in |v=73,J=2⟩ are trapped in the optical lattice, and that the lifetime in the lattice is limited by optical excitation by the lattice light. The molecule trapping time for a lattice depth of 15 atomic recoil energies is about 20 ms. We determine the trapping frequency by the lattice phase and amplitude modulation technique. It will now be possible to transfer the molecules to the rovibrational ground state |v=0,J=0⟩ in the presence of the optical lattice.

Dark resonances for ground-state transfer of molecular quantum gases

One possible way to produce ultracold, high-phase-space-density quantum gases of molecules in the rovibronic ground state is given by molecule association from quantum-degenerate atomic gases on a Feshbach resonance and subsequent coherent optical multi-photon transfer into the rovibronic ground state. In ultracold samples of Cs_2 molecules, we observe two-photon dark resonances that connect the intermediate rovibrational level |v=73,J=2> with the rovibrational ground state |v=0,J=0> of the singlet $X^1\Sigma_g^+$ ground state potential. For precise dark resonance spectroscopy we exploit the fact that it is possible to efficiently populate the level |v=73,J=2> by two-photon transfer from the dissociation threshold with the stimulated Raman adiabatic passage (STIRAP) technique. We find that at least one of the two-photon resonances is sufficiently strong to allow future implementation of coherent STIRAP transfer of a molecular quantum gas to the rovibrational ground state |v=0,J=0>.

Dark state experiments with ultracold, deeply-bound triplet molecules

We examine dark quantum superposition states of weakly bound Rb2 Feshbach molecules and tightly bound triplet Rb2 molecules in the rovibrational ground state, created by subjecting a pure sample of Feshbach molecules in an optical lattice to a bichromatic Raman laser field. We analyze, both experimentally and theoretically, the creation and dynamics of these dark states. Coherent wavepacket oscillations of deeply bound molecules in lattice sites, as previously observed by Lang et al. (Phys. Rev. Lett., 2008, 101, 133005), are suppressed due to laser-induced phase locking of molecular levels. This can be understood as the appearance of a novel multilevel dark state. In addition, the experimental methods developed help to determine important properties of our coupled atom/ laser system.

Precision molecular spectroscopy for ground state transfer of molecular quantum gases

One possibility for the creation of ultracold, high phase space density quantum gases of molecules in the rovibronic ground state relies on first associating weakly-bound molecules from quantum-degenerate atomic gases on a Feshbach resonance and then transferring the molecules via several steps of coherent two-photon stimulated Raman adiabatic passage (STIRAP) into the rovibronic ground state. Here, in ultracold samples of Cs2 Feshbach molecules produced out of ultracold samples of Cs atoms, we observe several optical transitions to deeply-bound rovibrational levels of the excited 0(u)+ molecular potentials with high resolution. At least one of these transitions, although rather weak, allows efficient STIRAP transfer into the deeply-bound vibrational level (see text for symbols)v = 73 > of the singlet X1 sigma(g)+ ground state potential, as recently demonstrated (J. G. Danzl, E. Haller, M. Gustavsson, M. J. Mark, R. Hart, N. Bouloufa, O. Dulieu, H. Ritsch, and H.-C. Nägerl, Science, 2008, 321, 1062). From this level, the rovibrational ground state (see text for symbols)v = 0, J = 0 > can be reached with one more transfer step. In total, our results show that coherent ground state transfer for Cs2 is possible using a maximum of two successive two-photon STIRAP processes or one single four-photon STIRAP process.

Ultracold polar molecules near quantum degeneracy

We report the creation and characterization of a near quantum-degenerate gas of polar 40K-87Rb molecules in their absolute rovibrational ground state. Starting from weakly bound heteronuclear KRb Feshbach molecules, we implement precise control of the molecular electronic, vibrational, and rotational degrees of freedom with phase-coherent laser fields. In particular, we coherently transfer these weakly bound molecules across a 125 THz frequency gap in a single step into the absolute rovibrational ground state of the electronic ground potential. Phase coherence between lasers involved in the transfer process is ensured by referencing the lasers to two single components of a phase-stabilized optical frequency comb. Using these methods, we prepare a dense gas of 4 x 10(4) polar molecules at a temperature below 400 nK. This fermionic molecular ensemble is close to quantum degeneracy and can be characterized by a degeneracy parameter of T/T(F) = 3. We have measured the molecular polarizability in an optical dipole trap where the trap lifetime gives clues to interesting decay mechanisms. Given the large measured dipole moment of the KRb molecules of 0.5 Debye, the study of quantum degenerate molecular gases interacting via strong dipolar interactions is now within experimental reach. PACS numbers: 37.10.Mn, 37.10.Pq.

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.

Molecular Beam Collisions with a Magnetically Trapped Target

Cold, neutral hydroxyl radicals are Stark decelerated and efficiently loaded into a permanent magnetic trap. The OH molecules are trapped in the rovibrational ground state at a density of approximately 10;{6} cm;{-3} and temperature of 70 mK. Collision studies between the trapped OH sample and supersonic beams of atomic He and molecular D2 determine absolute collision cross sections. The He-OH and D2-OH center-of-mass collision energies are tuned from 60 cm;{-1} to 230 cm;{-1} and 145 cm;{-1} to 510 cm;{-1}, respectively, yielding evidence of quantum threshold scattering and resonant energy transfer between colliding particles.

Ultracold Triplet Molecules in the Rovibrational Ground State

We report here on the production of an ultracold gas of tightly bound Rb2 triplet molecules in the rovibrational ground state, close to quantum degeneracy. This is achieved by optically transferring weakly bound Rb2 molecules to the absolute lowest level of the ground triplet potential with a transfer efficiency of about 90%. The transfer takes place in a 3D optical lattice which traps a sizeable fraction of the tightly bound molecules with a lifetime exceeding 200 ms.

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.

A High Phase-Space-Density Gas of Polar Molecules

A quantum gas of ultracold polar molecules, with long-range and anisotropic interactions, not only would enable explorations of a large class of many-body physics phenomena but also could be used for quantum information processing. We report on the creation of an ultracold dense gas of potassium-rubidium (40K87Rb) polar molecules. Using a single step of STIRAP (stimulated Raman adiabatic passage) with two-frequency laser irradiation, we coherently transfer extremely weakly bound KRb molecules to the rovibrational ground state of either the triplet or the singlet electronic ground molecular potential. The polar molecular gas has a peak density of 10(12) per cubic centimeter and an expansion-determined translational temperature of 350 nanokelvin. The polar molecules have a permanent electric dipole moment, which we measure with Stark spectroscopy to be 0.052(2) Debye (1 Debye = 3.336 x 10(-30) coulomb-meters) for the triplet rovibrational ground state and 0.566(17) Debye for the singlet rovibrational ground state.

Formation of deeply bound molecules via chainwise adiabatic passage

We suggest and analyze a 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 multistate chainwise stimulated Raman adiabatic passage 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 $^{87}\mathrm{Rb}_{2}$ starting from an initial Feshbach molecular state and taking into account major decay mechanisms due to inelastic atom-molecule and molecule-molecule collisions. Numerical analysis suggests a transfer efficiency $g90%$, even in the presence of strong collisional relaxation as are present in a high density atomic gas.

A STATE-TO-STATE QUANTUM DYNAMICAL STUDY OF THE H + HBr REACTION

The time-dependent wave packet method was used to calculate the state-to-state differential cross sections for abstraction and exchange processes in the title reaction on the Kurosaki–Takayanagi potential energy surface [Kurosaki Y, Takayanagi T, J Chem Phys119:7838, 2003], with the reactant HBr initially in the ground rovibrational state. It is found that the trend in the product distributions is similar for abstraction and exchange processes, but the differential cross sections are very different. For the exchange reaction, the product is mainly scattered in the backward hemisphere for collision energy up to 2.0 eV, although forward scattering gradually shows up in high collision energies. While for abstraction reaction, the differential cross section changes substantially with the collision energy, moving from predominantly backward peaked at low collision energy to predominantly forward peaked at high collision energy. The rovibrational state resolved differential cross section at collision energy of 2.0 eV exhibits two peaks for the abstraction reaction, one is around the angle of 50°, and the other at 0°. It is found that the peaks around 50°, are below the corresponding maximum j' lines provided by the kinematic constraint model, while the forward-scattered peaks straddle both sides of the kinematic limit, and are likely contributed from both the direct and the migratory reaction mechanisms as proposed by Zare and coworkers.

The three-dimensional nonadiabatic dynamics calculation of DH2+ and HD2+ systems by using the trajectory surface hopping method based on the Zhu–Nakamura theory

A theoretical investigation on the nonadiabatic processes of the full three-dimensional D(+)+H(2) and H(+)+D(2) reaction systems has been performed by using trajectory surface hopping (TSH) method based on the Zhu-Nakamura (ZN) theory. This ZN-TSH method refers to not only classically allowed hops but also classically forbidden hops. The potential energy surface constructed by Kamisaka et al. is employed in the calculation. A new iterative method is proposed to yield the two-dimensional seam surface from the topography of the adiabatic potential surfaces, in which the inconvenience of directly solving the first-order partial differential equation is avoided. The cross sections of these two systems are calculated for three competing channels of the reactive charge transfer, the nonreactive charge transfer, and the reactive noncharge transfer, for ground rovibrational state of H(2) or D(2). Also, this study provides reaction probabilities of these three processes for the total angular momentum J=0 and ground initial vibrational state of H(2) or D(2). The calculated results from ZN-TSH method are in good agreement with the exact quantum calculations and the experimental measurements.

Quasiclassical trajectory calculations of the OH+NO2 association reaction on a global potential energy surface

We report a full-dimensional potential energy surface (PES) for the OH+NO(2) reaction based on fitting more than 55,000 energies obtained with density functional theory-B3LYP6-311G(d,p) calculations. The PES is invariant with respect to permutation of like nuclei and describes all isomers of HOONO, HONO(2), and the fragments OH+NO(2) and HO(2)+NO. Detailed comparison of the structures, energies, and harmonic frequencies of various stationary points on the PES are made with previous and present high-level ab initio calculations. Two hydrogen-bond complexes are found on the PES and confirmed by new ab initio CASPT2 calculations. Quasiclassical trajectory calculations of the cross sections for ground rovibrational OH+NO(2) association reactions to form HOONO and HONO(2) are done using this PES. The cross section to form HOONO is larger than the one to form HONO(2) at low collision energies but the reverse is found at higher energies. The enhancement of the HOONO complex at low collision energies is shown to be due, in large part, to the transient formation of a H-bond complex, which decays preferentially to HOONO. The association cross sections are used to obtain rate constants for formation of HOONO and HONO(2) for the ground rovibrational states in the high-pressure limit.

Designing spin-1 lattice models using polar molecules

We describe how to design a large class of always on spin-1 interactions between polar molecules trapped in an optical lattice. The spin degrees of freedom correspond to the hyperfine levels of a ro-vibrational ground state molecule. Interactions are induced using a microwave field to mix ground states in one hyperfine manifold with the spin entangled dipole–dipole coupled excited states. Using multiple fields, anistropic models in one, two, or three dimensions can be built with tunable spatial range. An illustrative example in one-dimension is the generalized Haldane model, which at a specific parameter has a gapped valence bond solid ground state. The interaction strengths are large compared to decoherence rates and should allow for probing the rich phase structure of strongly correlated systems, including dimerized and gapped phases.

Photoassociation adiabatic passage of ultracold Rb atoms to form ultracoldRb2molecules

We theoretically explore photoassociation by adiabatic passage of two colliding cold $^{85}\mathrm{Rb}$ atoms in an atomic trap to form an ultracold ${\mathrm{Rb}}_{2}$ 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 $\ensuremath{\sim}2\ifmmode\times\else\texttimes\fi{}{10}^{7}$ pulses of moderate intensities, each lasting $\ensuremath{\sim}750\phantom{\rule{0.3em}{0ex}}\mathrm{ns}$, can photoassociate a large fraction of the atomic ensemble at temperature of $100\phantom{\rule{0.3em}{0ex}}\ensuremath{\mu}\mathrm{K}$ and density of ${10}^{11}\phantom{\rule{0.3em}{0ex}}\text{atoms}∕{\mathrm{cm}}^{3}$. 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 rovibrational state.

State-to-state quantum reactive scattering for four-atom chemical reactions: Differential cross section for the H+H2O→H2+OH abstraction reaction

The time-dependent wave packet method was extended to calculate the state-to-state differential cross section for the title four-atom abstraction reaction with H2O in the ground rovibrational state. One spectator OH bond length was fixed in the study, but the remaining five degrees of freedom were treated exactly. It was found that (a) the differential cross section changes from being strongly backward peaked at low collision energy to sideward scattering at E = 1.4 eV, and (b) the rotational state-resolved differential cross section for H2 differs substantially from that for OH.