Rovibronic States Research Articles

External field control of spin-dependent rotational decoherence of ultracold polar molecules

We determine trapping conditions for ultracold polar molecules, where pairs of internal states experience identical trapping potentials. Such conditions could ensure that detrimental effects of inevitable inhomogeneities across an ultracold sample are significantly reduced. In particular, we investigate the internal rovibronic and hyperfine quantum states of ultracold fermionic ground-state 40K87Rb polar molecules, when static magnetic, static electric and trapping laser fields are simultaneously applied. Understanding the effect of changing the relative orientation or polarisation of these three fields is of crucial importance for the creation of decoherence-free subspaces built from two or more rovibronic states. Moreover, we evaluate the induced dipole moment of the molecule in the presence of these fields, which will allow control of interactions between molecules in different sites of an optical lattice, and study the influence of the interaction anisotropy on the ability to entangle polar molecules.

On the Calculation of Resonances in Pre-Born–Oppenheimer Molecular Structure Theory

The main motivation for this work is the exploration of rotational–vibrational states corresponding to electronic excitations in a pre-Born–Oppenheimer quantum theory of molecules. These states are often embedded in the continuum of the lower-lying dissociation channel of the same symmetry and thus are thought to be resonances. To calculate rovibronic resonances, the pre-Born–Oppenheimer variational approach of [J. Chem. Phys. 2012, 137, 024104], based on the usage of explicitly correlated Gaussian functions and the global vector representation, is extended with the complex coordinate rotation method. The developed computer program is used to calculate resonance energies and widths for the three-particle positronium anion, Ps(–), and the four-particle positronium molecule, Ps(2). Furthermore, the excited bound and resonance rovibronic states of the four-particle H2 molecule are also considered. Resonance energies and widths are estimated for the lowest-energy resonances of H(2) beyond the b (3)∑(u)(+) continuum.

Communication: State-to-state photodissociation study by the two-color VUV-VUV laser pump-probe time-slice velocity-map-imaging-photoion method

We demonstrate that combining two independently tunable vacuum ultraviolet (VUV) lasers and the time-slice velocity-map-imaging-photoion (VMI-PI) method allows the rovibronically state-selected photodissociation study of CO in the VUV region along with the state-selective detection of product C((3)P(0,1,2)) using the VUV-UV (1+1') resonance-enhanced photoionization and the VUV Rydberg autoionization methods. Both tunable VUV lasers are generated based on the two-photon resonance-enhanced four-wave mixing scheme using a pulsed rare gas jet as the nonlinear medium. The observed fine-structure distributions of product C((3)P(J)), J = 0, 1, and 2, are found to depend on the CO rovibronic state populated by VUV photoexcitation. The branching ratios for C((3)P0) + O((3)P(J)): C((3)P0) + O((1)D2), C((3)P1) + O((3)P(J)): C((3)P1) + O((1)D2), and C((3)P2) + O((3)PJ): C((3)P2) + O((1)D2), which were determined based on the time-slice VMI-PI measurements of C(+) ions formed by J-state selective photoionization sampling of C((3)P(0,1,2)), also reveal strong dependences on the spin-orbit state of C((3)P(0,1,2)). By combining the measured branching ratios and fine-structure distributions of C((3)P(0,1,2)), we have determined the correlated distributions of C((3)P(0,1,2)) accompanying the formation of O((1)D2) and O((3)P(J)) produced in the VUV photodissociation of CO. The success of this demonstration experiment shows that the VUV photodissociation pump-VUV photoionization probe method is promising for state-to-state photodissociation studies of many small molecules, which are relevant to planetary atmospheres as well as fundamental understanding of photodissociation dynamics.

New Insight into CO Photodesorption from C60

We report on new results concerning the interaction of CO with C(60) in the electronic ground state and an electronically excited state. We found that the energetically most favorable geometries are vertical or horizontal in the ground state but in the excited state the molecule is tilted by about 40°. The two-dimensional potential energy surfaces of these states were used to simulate the photodesorption process induced by a short laser-pulse. An interesting desorption mechanism was found, leading to a bimodal velocity distribution for each rotational quantum state if the molecule starts from the rovibronic ground state.

Towards the production of ultracold ground-state RbCs molecules: Feshbach resonances, weakly bound states, and the coupled-channel model

We have studied interspecies scattering in an ultracold mixture of ${}^{87}$Rb and ${}^{133}$Cs atoms, both in their lowest-energy spin states. The three-body loss signatures of 30 incoming $s$- and $p$-wave magnetic Feshbach resonances over the range 0 to 667 G have been cataloged. Magnetic field modulation spectroscopy was used to observe molecular states bound by up to 2.5 $\text{MHz}\ifmmode\times\else\texttimes\fi{}h$. We have created RbCs Feshbach molecules using two of the resonances. Magnetic moment spectroscopy along the magnetoassociation pathway from 197 to 182 G gives results consistent with the observed and calculated dependence of the binding energy on magnetic field strength. We have set up a coupled-channel model of the interaction and have used direct least-squares fitting to refine its parameters to fit the experimental results from the Feshbach molecules, in addition to the Feshbach resonance positions and the spectroscopic results for deeply bound levels. The final model gives a good description of all the experimental results and predicts a large resonance near 790 G, which may be useful for tuning the interspecies scattering properties. Quantum numbers and vibrational wave functions from the model can also be used to choose optimal initial states of Feshbach molecules for their transfer to the rovibronic ground state using stimulated Raman adiabatic passage.

Theoretical Study of the Rovibronic States of CaO

The spin-rovibronic energy levels of CaO, which result from the couplings of X 1Σ +, a 3 Π, A ′1 Π, b 3Σ +, and A 1Σ + low-lying electronic states, are determined from wave packet time propagations and Prony analysis. The electronic potentials were taken from our previous study [Chem. Phys., 386, 50 (2011)]. The spin-orbit and L ^ coupling functions were determined by CASSCF and MRCI calculations. The effects of spin-orbit coupling on vibrational levels were analyzed in the Ω = 0 +, 0 −, 1 coupling schemes. All spin-vibronic energy levels associated with the a 3 Π, A ′1 Π, b 3Σ +, and A 1Σ + states were determined up to 16 000 cm −1 above the electronic ground-state minimum. The results obtained from the spin-orbit coupling functions are in remarkable agreement with the experimental data extracted using a deperturbation procedure. The final energies calculated for J = 2 and J = 25 are used to compare the experimental observations concerning the X 1Σ +− A 1Σ + transition.

Laser-induced fluorescence studies of HfF+ produced by autoionization

Autoionization of Rydberg states of HfF, prepared using the optical-optical double resonance technique, holds promise to create HfF(+) in a particular Zeeman level of a rovibronic state for an electron electric dipole moment search. We characterize a vibronic band of Rydberg HfF at 54 cm(-1) above the lowest ionization threshold and directly probe the state of the ions formed from this vibronic band by performing laser-induced fluorescence on the ions. The Rydberg HfF molecules show a propensity to decay into only a few ion rotational states of a given parity and are found to preserve their orientation qualitatively upon autoionization. We show empirically that we can create 30% of the total ion yield in a particular ∣J(+), M(+)<linear span> state and present a simplified model describing autoionization from a given Rydberg state that assumes no angular dynamics.

Rovibrational eigenenergy structure of the [H,C,N] molecular system

The vibrational-rotational eigenenergy structure of the [H,N,C] molecular system is one of the key features needed for a quantum mechanical understanding of the HCN⇌HNC model reaction. The rotationless vibrational structure corresponding to the multidimensional double well potential energy surface is well established. The rotational structure of the bending vibrational states up to the isomerisation barrier is still unknown. In this work the structure of the rotational states for low and high vibrational angular momentum is described from the ground state up to the isomerisation barrier using hot gas molecular high resolution spectroscopy and rotationally assigned ab initio rovibronic states. For low vibrational angular momentum the rotational structure of the bending excitations splits in three regions. For J < 40 the structure corresponds to that of a typical linear molecule, for 40 < J < 60 has an approximate double degenerate structure and for J > 60 the splitting of the e and f components begins to decrease and the rotational constant increases. For states with high angular momentum, the rotational structure evolves into a limiting structure for v(2) > 7--the molecule is locked to the molecular axis. For states with v(2) > 11 the rotational structure already begins to accommodate to the lower rotational constants of the isomerisation states. The vibrational energy begins to accommodate to the levels above the barrier only at high vibrational excitations of v(2) > 22 just above the barrier whereas this work shows that the rotational structure is much more sensitive to the double well structure of the potential energy surface. The rotational structure already experiences the influence of the barrier at much lower energies than the vibrational one.

Production of a dual-species Bose-Einstein condensate of Rb and Cs atoms

We report the simultaneous production of Bose-Einstein condensates (BECs) of 87Rb and 133Cs atoms in separate optical traps. The two samples are mixed during laser cooling and loading but are separated by 400 μm for the final stage of evaporative cooling. This is done to avoid considerable interspecies three-body recombination, which causes heating and evaporative loss. We characterize the BEC production process, discuss limitations, and outline the use of the dual-species BEC in future experiments to produce rovibronic ground state molecules, including a scheme facilitated by the superfluid-to-Mott-insulator (SF-MI) phase transition.

Extended permutation-inversion groups for simultaneous treatment of the rovibronic states of trans-acetylene, cis-acetylene, and vinylidene

The electronic ground state potential surface of acetylene (H C C H) has a minimum at the linear conformation, but the excited electronic states may have potential minima at a variety of nonlinear equilibrium shapes. This work is concerned with the group theoretical ideas necessary to treat simultaneously the symmetry properties of rovibronic states associated with three different planar acetylene equilibrium configurations, namely trans bent acetylene, cis bent acetylene, and vinylidene (H 2C C). We make use of three different kinds of groups: (i) point groups, (ii) permutation-inversion (PI) groups, and (iii) extended PI groups. The PI group is G 4 or G 8, depending on whether C H bond breaking is impossible (no bent acetylene ↔ vinylidene interconversion) or possible. The extended PI groups are G 4 ( 2 ) and G 8 ( 2 ) , respectively, when the only large amplitude motions are the CCH bends at each end of the molecule, and G 4 ( 8 ) and G 8 ( 8 ) , respectively, when internal rotation is added as a third large amplitude motion. Applied to acetylene, the results indicate that there will be no splittings of the rovibronic levels unless CH bond breaking occurs. Even without bond breaking, however, states of the cis and trans isomers just below their interconversion barrier will show “staggerings” in their K-structures, i.e., a given vibrational level will have three tunneling components at slightly different energies: one component will have levels with K = 4 n only (where n is an integer), a second component will have levels with K = 4 n + 2 only, and the third will have only odd- K levels. New experimental results for the S 1–cis electronic state of acetylene [21] are reviewed, and are found to be consistent with the group theory in so far as comparison is possible.

Ab initio rovibronic states of the thioketenyl radical in its X2Π electronic ground state

We present an ab initio study of the thioketenyl (HCCS) radical in its degenerate X(2)Π electronic ground state. All rotational and vibrational degrees of freedom are taken into account including the electronic orbital and spin angular momenta. The structure of the rovibronic levels and the nature of the corresponding wave functions show resonances even at very low energies due to strong couplings between the bending, rotation, and spin terms in the Hamiltonian. Assignments from the dominant contributions of the eigenvectors are discussed in parallel with previously published data. The rotational structures for the first excited vibronic states are computed as well as transition intensities for the fundamental one.

Ultracold and dense samples of ground-state molecules in lattice potentials

We produce an ultracold and dense sample of rovibronic ground state Cs2 molecules close to the regime of quantum degeneracy, in a single hyperfine level, in the presence of an optical lattice. The molecules are individually trapped, in the motional ground state of an optical lattice well, with a lifetime of 8 s. For preparation, we start with a zero-temperature atomic Mott-insulator state with optimized double-site occupancy and efficiently associate weakly-bound dimer molecules on a Feshbach resonance. Despite extremely weak Franck-Condon wavefunction overlap, the molecules are subsequently transferred with >50% efficiency to the rovibronic ground state by a stimulated four-photon process. Our results present a crucial step towards the generation of Bose-Einstein condensates of ground-state molecules and, when suitably generalized to polar heteronuclear molecules such as RbCs, the realization of dipolar many-body quantum-gas phases in periodic potentials.

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 (A(1)Σ(+)-b(3)Π)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 X(1)Σ(+) ground state to be D = 3811.5755(16) cm(-1), 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.

ChemInform Abstract: Photodissociation Dynamics of 3-Cyclopentenone: Using the Impact Parameter Distribution as a Criterion for Concertedness.

The cyclic ketone 3-cyclopentenone has been dissociated in a molecular beam with a pulsed excimer laser to yield butadiene and CO, and the CO product state distribution has been measured using vacuum ultraviolet laser-induced fluorescence with full rovibronic state resolution. It is found that the CO rotational temperatures in =0 and 1 are 3500±140 and 7500±400 K, respectively, and that the vibrational distribution is characterized by a temperature of 1750±200 K

Near infrared emission spectrum of H 13CN

The emission spectrum of H 13CN at 1370 K has been recorded with a hot gas high resolution FT-IR emission apparatus [1] in the wavenumber region of 6000 – 6800 cm - 1 with a resolution of 0.044 cm - 1 . This work reports the analysis of 50 subbands for the H 13CN isotopologue of hydrogen cyanide in the 2 ν 1 wavenumber region. 23 rovibronic states of H 13CN including the v 1 v 2 l v 3 = 26 6 0 rovibronic states at 10580 cm - 1 have been characterized for the first time and for seven other states it was possible to improve the existing spectroscopic constants substantially. The dense emission spectrum was analyzed with the spectrum analysis software SyMath™ implemented in the Mathematica™ computer algebra system [1].

An ultracold high-density sample of rovibronic ground-state molecules in an optical lattice

Control over all internal and external degrees of freedom of molecules at the level of single quantum states will enable a series of fundamental studies in physics and chemistry. In particular, samples of ground-state molecules at ultralow temperatures and high number densities will allow novel quantum-gas studies and future applications in quantum information science. However, high phase-space densities for molecular samples are not readily attainable as efficient cooling techniques such as laser cooling are lacking. Here we produce an ultracold and dense sample of molecules in a single hyperfine level of the rovibronic ground state with each molecule individually trapped in the motional ground state of an optical lattice well. Starting from a zero-temperature atomic Mott-insulator state with optimized double-site occupancy, weakly-bound dimer molecules are efficiently associated on a Feshbach resonance and subsequently transferred to the rovibronic ground state by a stimulated four-photon process with >50 % efficiency. The molecules are trapped in the lattice and have a lifetime of 8 s. Our results present a crucial step towards Bose-Einstein condensation of ground-state molecules and, when suitably generalized to polar heteronuclear molecules, the realization of dipolar quantum-gas phases in optical lattices.

Controlling the Hyperfine State of Rovibronic Ground-State Polar Molecules

We report the preparation of a rovibronic ground-state molecular quantum gas in a single hyperfine state and, in particular, the absolute lowest quantum state. This addresses the last internal degree of freedom remaining after the recent production of a near quantum degenerate gas of molecules in their rovibronic ground state, and provides a crucial step towards full control over molecular quantum gases. We demonstrate a scheme that is general for bialkali polar molecules and allows the preparation of molecules in a single hyperfine state or in an arbitrary coherent superposition of hyperfine states. The scheme relies on electric-dipole, two-photon microwave transitions through rotationally excited states and makes use of electric nuclear quadrupole interactions to transfer molecular population between different hyperfine states.

Bound states of the OH(Π2)–HCl complex on ab initio diabatic potentials

The bound states of the open-shell OH((2)Pi)-HCl complex were calculated in four dimensions with a diabatic model using electronic states that correlate asymptotically with the ground and excited spin-orbit states of the OH((2)Pi) fragment and the ground state of the HCl fragment. The ab initio diabatic potentials and their analytic expansion applied in these calculations were obtained earlier by Wormer et al. [J. Chem. Phys. 122, 244325 (2005)]. In addition to the four-dimensional calculations, we considered a (3+1)-dimensional model in which the intermolecular distance coordinate R is adiabatically separated from the remaining coordinates. Both models include the important spin-orbit coupling in the OH fragment. Energy levels and parity splittings were computed for a total angular momentum of J=1/2 and 3/2; rotational constants and other spectroscopic parameters were extracted from these calculations. The vibrationally averaged geometry in the ground state of the complex is planar and this state is more or less localized near the minimum in the lowest adiabatic potential with binding energy D(e)=1123 cm(-1); the dissociation energy D(0) with respect to OH((2)Pi(3/2)) and HCl is found to be 685 cm(-1). The splitting between the (2)Pi(3/2) and (2)Pi(1/2) spin-orbit states of free OH is largely reduced by the anisotropic interaction with HCl through the off-diagonal diabatic coupling potential and these states are strongly mixed. Low lying rovibronic states that correlate with the OH((2)Pi(3/2)) ground state were found at 14 cm(-1) for total angular momentum projection quantum number |Omega|=3/2 and 26 cm(-1) for |Omega|=1/2, relative to the ground state with |Omega|=1/2. The OH-HCl stretch fundamental frequency equals to 93.6 cm(-1), the lowest bend excited states (involving a coupled bend motion of both fragments) were found in the region of 150-160 cm(-1) above the ground state. Especially in the excited states important nonadiabatic effects are observed that involve both of the asymptotically degenerate adiabatic electronic states. In some of these excited states the vibrationally averaged geometry is nonplanar.

Four-Component Relativistic Coupled Cluster and Configuration Interaction Calculations on the Ground and Excited States of the RbYb Molecule

We present high-level four-component coupled cluster and multireference configuration interaction calculations of potential energy curves, dipole moment, Franck-Condon factors and spectroscopic constants of the newly formed RbYb molecule. From finite-field calculations we obtain an electric dipole moment for RbYb of almost 1 D. In combination with its magnetic dipole moment this makes RbYb an excellent candidate for trapping and for studying dipolar interaction in the ultracold regime. Significant Franck-Condon factors are found between the rovibronic ground state and the lowest rovibrational levels of the first excited 2Sigma1/2+ state but also between a broad range of rovibrational levels of the 2Pi1/2 and 2Pi3/2 states. This allows for several two-step approaches to reach the rovibronic ground state after initial photoassociation.

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>.