-state of the heteronuclear polar molecules NaCs, KCs, and RbCs. These molecules are of current interest in experiments at ultra-cold conditions to explore the effects of the strong dipole-dipole forces on the collective many-body quantum behavior. New quantum phenomena are also anticipated in systems consisting of atomic species with different fermion/boson statistics. The model parameters are obtained by simultaneously fitting all five of the parameters to the extensive LIF-Fourier transform spectroscopy published by Tiemann and collaborators [e.g., Docenko et al. J. Phys. B: At., Mol. Opt. Phys. 39, S929-S943 (2006)], who also report best fit potential curves. Although the new potentials are in good agreement with the earlier potentials, they have the advantage that they are continuous over the entire range of internuclear distances and have the correct long-range behavior. The scattering lengths for all isotope combinations show good agreement with dedicated experiments where available. The new potentials are also in excellent agreement with combining rules based on the potentials of the homonuclear systems.
-state of the heteronuclear polar molecules NaCs, KCs, and RbCs. These molecules are of current interest in experiments at ultra-cold conditions to explore the effects of the strong dipole-dipole forces on the collective many-body quantum behavior. New quantum phenomena are also anticipated in systems consisting of atomic species with different fermion/boson statistics. The model parameters are obtained by simultaneously fitting all five of the parameters to the extensive LIF-Fourier transform spectroscopy published by Tiemann and collaborators [e.g., Docenko et al. J. Phys. B: At., Mol. Opt. Phys. 39, S929-S943 (2006)], who also report best fit potential curves. Although the new potentials are in good agreement with the earlier potentials, they have the advantage that they are continuous over the entire range of internuclear distances and have the correct long-range behavior. The scattering lengths for all isotope combinations show good agreement with dedicated experiments where available. The new potentials are also in excellent agreement with combining rules based on the potentials of the homonuclear systems.
A semiempirical potential energy curve for the a3Σ+-state of the KRb molecule with only five parameters is reported. The potential is continuous over the entire range of internuclear distances and has the correct long-range attractive dispersion potential from established theory. The potential provides an equally good fit of the laser induced fluorescence Fourier transform spectroscopic data of Pashov et al. [Phys. Rev. A 76, 022511 (2007)] as their multi-parameter potential. The new potential is supported by the good agreement of the well parameters De, Re and the harmonic vibrational constant ωe with combining-rule estimates. The scattering lengths for all six isotopologues are also in excellent agreement with experiment with a 0.2% adjustment within theoretical uncertainty of the leading dispersion coefficient C6. An analysis of the harmonic vibrational constant ωe and the constant ωexe of the potential of Pashov et al. reveals a significant difference to the present potential which turned out to be due to an oscillatory deviation in their potential in the vicinity of the potential minimum. The new potential is, thus, the best available because its simplicity is ideal for further applications.
Obtaining ultracold samples of dipolar molecules is a current challenge which requires an accurate knowledge of their electronic properties to guide the ongoing experiments. Alkali hydride molecules have permanent dipole significantly larger than those of mixed alkali species and, as pointed out by Taylor-Juarros et al. [Eur. Phys. J. D 31, 213 (2004)] and by Juarros et al. [Phys. Rev. A 73, 041403 (2006)], are thus good candidates for molecule formation. In this paper, using a standard quantum chemistry approach based on pseudopotentials for atomic core representation, large Gaussian basis sets, and effective core polarization potential, we systematically investigate the electronic properties of the alkali hydrides LiH to CsH, in order to discuss general trends of their behavior. We computed (for the first time for NaH, KH, RbH, and CsH) the variation of their static polarizability with the internuclear distance. Moreover, in addition to potential curves, we determine accurate values of permanent and transition dipole moments for ground and excited states depending on the internuclear distance. The behavior of electronic properties of all alkali hydrides is compared to each other, in the light of the numerous other data available in the literature. Finally, the influence of the quality of the representation of the hydrogen electronic affinity in the approach on the results is discussed.
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 calculate permanent dipole moments and transition dipole moments for excited states for alkali dimers NaK, NaRb and NaCs using a standard quantum chemistry approach based on pseudopotentials for atomic core representation, Gaussian basis sets, and effective terms for core polarization effects. We provide an extensive set of data concerning transitions among the first seven molecular states of each symmetry 1Σ+, 3Σ+, 1Π, 3Π. The accuracy of our results is generally improved compared to previous similar calculations on NaK, while they are found to be in good agreement with the few NaRb states calculated with other methods. Results for NaCs transition dipole moments are given here for the first time.
A model for determining the hyperfine structure of the excited electronic states of diatomic bialkali heteronuclear molecules is formulated from the atomic hyperfine interactions and is applied to the case of bosonic 39KCs and fermionic 40KCs molecules. The hyperfine structure of the potential-energy curves of the states correlated to the K(4s2S1/2)+Cs(6p2P1/2,3/2) dissociation limits is described in terms of different coupling schemes depending on the internuclear distance R. These results provide a step in the calculation of the hyperfine structure of rovibrational levels of these excited molecular states in the perspective of the identification of efficient paths for creating ultracold ground-state KCs molecules.
Ultracold diatomic molecules find application in quantum studies ranging from controlled chemistry and precision measurement physics to quantum many-body simulation and potentially quantum computing. Accurate knowledge of molecular properties is required to guide and explain ongoing experiments. Here, in an extensive and comparative study, we theoretically investigate the electronic properties of the ground-state diatomic molecules composed of alkali-metal (Li, Na, K, Rb, Cs, Fr) and alkaline-earth-metal (Be, Mg, Ca, Sr, Ba, Ra) atoms. We study 78 heteronuclear and homonuclear diatomic combinations, including 21 alkali-metal molecules in the ${X}^{1}{\mathrm{\ensuremath{\Sigma}}}^{+}$ and ${a}^{3}{\mathrm{\ensuremath{\Sigma}}}^{+}$ electronic states, 36 alkali-metal--alkaline-earth-metal molecules in the ${X}^{2}{\mathrm{\ensuremath{\Sigma}}}^{+}$ electronic state, and 21 alkaline-earth-metal molecules in the ${X}^{1}{\mathrm{\ensuremath{\Sigma}}}^{+}$ electronic state. We calculate potential energy curves, permanent electric dipole moments, and polarizabilities using the hierarchy of coupled-cluster methods up to CCSDTQ with large Gaussian basis sets and small-core relativistic energy-consistent pseudopotentials. We collect and analyze corresponding spectroscopic constants. We estimate computational uncertainties and compare the present values with previous experimental and theoretical data to establish a different theoretical benchmark. The presented results should be useful for further application of the studied molecules in modern ultracold physics and chemistry experiments.
Abstract Heteronuclear lithium-containing alkali dimers in their ground triplet state offer both electric and magnetic dipole moments, which arise from their unpaired electron distributions and make them suitable for exploring many-body quantum phenomena. Currently, no simple yet accurate analytical form exists to model the triplet interaction potentials of heavier Li-alkali pairs such as LiK, LiRb and LiCs. The Sheng-Tang–Toennies(STT) potential, containing merely two fitting parameters, has earlier successfully reproduced the lowest triplet potential curve of Li 2 and LiNa. In this work, we extend its application to predict the a 3 Σ + state interactions for the three dimers LiK, LiRb, and LiCs. The derived analytical potentials agree closely with high-level a b i n i t i o benchmarks and existing spectroscopic measurements over the complete range of internuclear separations. Our findings verify the robustness and portability of the STT model for representing triplet state potentials across heteronuclear alkali dimers that include lithium.