Spectroscopy and applications of the 3 3Σ+ electronic state of 39K85Rb.

We report new results on the spectroscopy of the 3 (3)Σ(+) electronic state of (39)K(85)Rb. The observations are based on resonance-enhanced multiphoton ionization of ultracold KRb molecules starting in vibrational levels v'' = 18-23 of the a (3)Σ(+) state and ionized via the intermediate 3 (3)Σ(+) state. The a-state ultracold molecules are formed by photoassociation of ultracold (39)K and (85)Rb atoms to the 3(0(+)) state of KRb followed by spontaneous emission. We discuss the potential applications of this state to future experiments, as a pathway for populating the lowest vibrational levels of the a state as well as the X state.

Spectroscopy of the double minimum 3 (3)ΠΩ electronic state of 39K85Rb.

We report the observation and analysis of the 3 (3)ΠΩ 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 ab initio potential curves. We have assigned the vibrational levels v' = 2-11 of the 3 (3)Π1,2 potentials and v' = 2-12 of the 3(3)Π0(+/-) potential. We compare our experimental observations of the 3 (3)ΠΩ state with predictions based on theoretical potentials. The observations are based on resonance enhanced multiphoton ionization of ultracold KRb in vibrational levels v" = 14-25 of the a (3)Σ(+) state. These a-state ultracold molecules are formed by photoassociation of ultracold (39)K and (85)Rb atoms to the 5(1) state of KRb followed by spontaneous emission to the a state.

Structure, energetics, and reactions of alkali tetramers.

Electronic structure calculations have been carried out for all possible alkali tetramers that can be formed from X(2) + X(2) → X(2)X(2), X(2) + Y(2) → X(2)Y(2), and XY + XY → X(2)Y(2) alkali dimer association reactions. Vibrationally stable rhombic (D(2h)) and planar (C(s)) structures are found for all possible tetramers formed from the alkali metals, Li to Cs. All tetramer formation reactions (from ground state singlet homonuclear or heteronuclear dimers) are found to be exothermic with binding energies ranging from 6282 cm(-1) for Li(2)Li(2) to 1985 cm(-1) for Cs(2)Cs(2). Extensive calculations, carried out at long-range for several reactant pairs, indicate that there are barrier-less pathways for the formation of tetramers from dimer association reactions. At low temperatures, direct formation of tetramers is unlikely, owing to the large exothermicity associated with these association reactions, but atom exchange reactions (X(2) + Y(2) ↔ XY + XY) are possible for some species.

Spectroscopic investigation of the A and 3 1Σ+ states of 39K85Rb.

By using a combination of molecular beam (MB) excitation spectra and two distinct ultracold molecule excitation spectra (UM+ and UM-), we have assigned high vibrational levels of the A and 3 (1)Σ(+) states from absorption spectra of the mutually strongly perturbed A (1)Σ(+) - 3 (1)Σ(+) - 1 (1)Π - 2 (3)Σ(+) - b (3)Π states of ultracold (39)K(85)Rb molecules in the energy region between 15,116 and 16,225 cm(-1) above the minimum of the ground X (1)Σ(+) state. The ultracold molecules (UM+ and UM-) are formed by radiative decay following photoassociation (PA) to a specific level of the 3(0(+)) state (UM+) or to a specific level of the 3(0(-)) state (UM-). We observe that the A and 3 (1)Σ(+) states are observable in the UM+ spectra, but absent from the UM- spectra. This is explained by considering Hund's case (c) selection rules and transition dipole moments between the upper excited A (1)Σ(+) (2(0(+))) state and the three Ω components (0(+), 0(-), and 1) at the ground-state dissociation limit. We propose further investigations of the extended potential wells of the A and 3 (1)Σ(+) states by combining short-range MB excitation spectra in a narrow Franck-Condon (FC) window near R(e) of the X (1)Σ(+) state, and long-range UM (and PA) excitation spectra, which have much larger FC windows.

Spectroscopic analysis of the coupled 1(1)Π, 2(3)Σ+ (Ω = 0-, 1), and b(3)Π (Ω = 0±, 1, 2) states of the KRb molecule using both ultracold molecules and molecular beam experiments.

We report the spectroscopic characterization of excited electronic states of KRb by combining spectra from molecular beam (MB) experiments with those from ultracold molecules (UM) formed by photoassociation (PA) of ultracold atoms. Spectra involving the 1(1)Π, 2(3)Σ(+), and b(3)Π states in a strongly perturbed region have been identified. This approach provides a powerful method to identify the vibrational levels of the excited electronic states perturbed globally by neighboring electronic states. This is because the two sets of spectra from the UM and the MB experiments probe the same energy region from very different initial electronic states. The UM experiments utilize high v'' levels of the a(3)Σ(+) state with large internuclear separations, while the MB experiments utilize low v'' levels of the ground X(1)Σ(+) state with near-equilibrium internuclear separations. Only the Ω = 1 levels of the 2(3)Σ(+) and b(3)Π states are observed in the MB spectra, while the Ω = 0(-), 1 levels of the 2(3)Σ(+) state and the Ω = 0(±), 1, 2 levels of the b(3)Π state are observed in the UM spectra.

Long range intermolecular interactions between the alkali diatomics Na(2), K(2), and NaK.

Long range interactions between the ground state alkali diatomics Na(2)-Na(2), K(2)-K(2), Na(2)-K(2), and NaK-NaK are examined. Interaction energies are first determined from ab initio calculations at the coupled-cluster with singles, doubles, and perturbative triples [CCSD(T)] level of theory, including counterpoise corrections. Long range energies calculated from diatomic molecular properties (polarizabilities and dipole and quadrupole moments) are then compared with the ab initio energies. A simple asymptotic model potential E(LR)=E(elec)+E(disp)+E(ind) is shown to accurately represent the intermolecular interactions for these systems at long range.

The D 1Sigma+ state of 7LiH: comparison of observations with vibronic theory.

The excited D (1)Sigma(+) electronic state of (7)LiH has been observed up to near its dissociation limit by a pulsed optical-optical double resonance fluorescence depletion spectroscopic technique. An extensive vibronic calculation has been performed with a diabatic approach with purely potential couplings involving a set of eight diabatic states of (1)Sigma(+) symmetry, corresponding to seven neutral states and one ionic state. Twenty-six new vibrational levels have been observed. Both the derived vibrational energy spacings and the vibronic ones are similarly irregular. The observed spectral linewidths and vibronic resonance widths are found to vary similarly with increasing energy. Observed asymmetric spectral lineshapes may be attributed to the strong radial couplings between the discrete levels of the D (1)Sigma(+) electronic state and the continuum states of the C (1)Sigma(+) electronic state. The mutual agreement between the spectral results and the vibronic results demonstrates that the D (1)Sigma(+) electronic state of (7)LiH is better characterized by the vibronic approach.

Improved dissociation energy of the 39K85Rb molecule.

The predissociation data for the 1 (1)Pi state of (39)K(85)Rb of Kasahara et al. [J. Chem. Phys. 111, 8857 (1999)] are combined with the recent determination of the long range C(6) coefficients of the predissociating 2 (3)Sigma(+) approximately 2(0(-)), 2(1) states [Wang et al., Eur. Phys. J. D31, 165 (2004) ] molecule: to infer a more precise dissociation energy of the (39)K(85)Rb molecule D(0)=4180.06+/-0.42 cm(-1) and D(e)=4217.91+/-0.42 cm(-1).

Photoassociation spectroscopy of ultracold Cs below the 6P(3/2) limit.

High precision photoassociation spectroscopy is performed in ultracold cesium gas, with detunings as large as 51 cm(-1) below the Cs(6S(1/2))+Cs(6P(3/2)) asymptote. Trap-loss fluorescence detection is used for detecting the photoassociation to excited state ultracold molecules. Long vibrational progressions are assigned to electronic states of 0(g) (-), 0(u) (+), and 1(g) symmetry. The spectral data are fitted to a LeRoy-Bernstein equation, in order to obtain the effective coefficients of the leading long-range interaction term (C(3)/R(3)) and the relative vibrational quantum numbers measured down from dissociation. Additionally we present evidence for perturbations between the 0(g) (-) state and the dark 2(u) state.

Radiative transition probabilities, lifetimes and dipole moments for the vibrational levels of the X1Sigma+ ground state of 39K85Rb.

Using a potential energy curve (based primarily on the RKR potential of Amiot and Verges [J. Chem. Phys. 112, 7068 (2000)]) and a dipole moment function (based primarily on ab initio calculations of Park et al. [Chem. Phys. 257, 135 (2000)]), we have calculated radiative transition probabilities (Einstein A coefficients), radiative lifetimes, and dipole moment expectation values involving all vibrational levels (for several rotational quantum numbers) of the X1Sigma+ ground state of 39K85Rb. We observe that the radiative lifetimes of vibrationally excited levels, in particular, are approximately 10(3)-10(6) seconds, far too long to be significant in most ultracold experiments involving 39K85Rb or its isotopomers. Comparison with other molecules (LiH and HF) suggests that simple scaling (A approximately mu2nu3 approximately tau(-1)) will predict similarly long lifetimes for many other heteronuclear molecules, e.g., RbCs.

Calculations of long-range potential wells for highly excited homonuclear and heteronuclear alkali dimers.

The weakly bound long-range potential curves between a highly excited alkali atom M(*)(n(e)s) and a ground state alkali atom M(n(g)s) are calculated using simple but reasonably accurate models for long-range dispersion and exchange interactions for all homonuclear and heteronuclear combinations. For K(2), where experimental results are available, the agreement is quite good (binding energies of observed vibrational levels within approximately 10%). We find that at least a zero-point vibrational level occurs for n(e)-n(g)

Photoassociation spectroscopy of ultracold Cs below the 6P1/2 limit.

We have performed high precision photoassociation spectroscopy of ultracold cesium gas. Using trap-loss fluorescence detection and controlling the background cesium pressure we were able to photoassociate atoms into excited states of ultracold molecules with large detunings up to 56 cm(-1) below the Cs(6S(1/2)) + Cs(6P(1/2)) atomic asymptote. Vibrational progressions are assigned to 0(g)(-), 0(u)(+), and 1(g) long-range states. By fitting the spectral data to the LeRoy-Bernstein expression, the effective coefficients of the leading long-range interactions and the vibrational quantum number at dissociation are obtained. In addition we have observed spectral perturbations between states of the same symmetry belonging to different asymptotes (6P(1/2) and 6P(3/2)). The perturbations are manifested through irregular vibrational level spacings and are especially pronounced in the 0(u)(+) symmetry. Many observed rotational levels indicate d- and higher partial wave contributions to the photoassociation cross section in the presence of trapping laser light, while spectral regions with only weak features suggest nodes in the lower state wave functions corresponding to the two ground state atoms asymptote.