By use of a free-energy model, the properties of a fluid composed of neutral atoms and diatomic molecules, positive ions and molecular ions, and an electron Fermi gas are calculated. The interactions include excluded volume, internal molecular binding, electron-neutral s-wave scattering, and screened Hartree interactions. For rubidium and cesium parametrizations, the vapor-liquid phase transitions with their critical points, the insulator-metal transitions, and the isothermal electrical conductivities and magnetic susceptibilities are obtained.
By use of a free-energy model, the properties of a fluid composed of neutral atoms and diatomic molecules, positive ions and molecular ions, and an electron Fermi gas are calculated. The interactions include excluded volume, internal molecular binding, electron-neutral s-wave scattering, and screened Hartree interactions. For rubidium and cesium parametrizations, the vapor-liquid phase transitions with their critical points, the insulator-metal transitions, and the isothermal electrical conductivities and magnetic susceptibilities are obtained.
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.
Studies of anions are inherently more challenging than investigations of neutrals and cations because of the diffuse and weakly bound character of an anionic electron. Here, we present a comprehensive computational examination of ground-state diatomic molecular anions composed of alkali-metal (Li, Na, K, Rb, Cs, Fr) and alkaline-earth-metal (Be, Mg, Ca, Sr, Ba, Ra) atoms. We study 21 alkali-metal diatomic anions in the X2Σ+ electronic state and 36 alkali-metal--alkaline-earth-metal diatomic anions in the X1Σ+ electronic state. The calculations employ a hierarchy of the coupled cluster methods, combined with large Gaussian basis sets and small-core relativistic energy-consistent pseudopotentials for heavier elements. We compute potential energy curves, permanent electric dipole moments, and static polarizabilities, and we assess convergence and uncertainties of our results. Additionally, using the multireference configuration interaction and equation-of-motion electron-attachment coupled cluster methods, we investigate excited electronic states of alkali-metal molecular anions, including valence-bound and dipole-bound states. We predict crossings between ground neutral and excited anionic states, which may enhance resonant electron attachment and subsequent anion dissociation. This finding may be relevant for experiments with mixtures of ultracold ground-state alkali-metal molecules and Rydberg atoms.
In this work, the binding energy of three alkali metal molecules, namely, lithium-7 (7Li2), sodium-23 (23Na2), and potassium-39 (39K2), is calculated in both free space and the vapor phase. In free space, the Lippmann–Schwinger equation is solved for negative-definite eigenenergies using a highly effective matrix-inversion method with a symmetrized kernel. In the vapor, two medium effects are taken into account: the effective atomic mass, which is somewhat larger than the “bare” mass and therefore enhances the binding; and the effective binary interaction, with less overall attraction than the “bare” interaction. In free space, the binding energies of the respective molecules are, in units of (103 K), 5.304, 2.936, and 2.522. The corresponding experimental results are 6.150 × 103, 4.275 ×103, and 4.275 × 103 K. The results in the vapor phase are by and large somewhat lower than those in free space.
The thermodynamic properties of a nonrelativistic free-electron Fermi gas is of fundamental interest in condensed matter physics. Properties previously studied in three-dimensions (3D) in the low- and high-temperature limits include the internal energy, heat capacity, zero-field magnetic spin susceptibility, and pressure. Here we report solutions for the temperature dependence spanning these two temperature regimes of the chemical potential, internal energy, magnetic susceptibility, and the heat capacity at constant volume in 1D, 2D, and 3D. Also calculated are the pressure, enthalpy, heat capacity at constant pressure, isothermal compressibility, and thermal expansion coefficient versus temperature in 2D and 3D. Of primary interest here are the detailed dimension-dependent crossovers of these properties between the degenerate and nondegenerate temperature regime, which are graphically illustrated for each of the above properties.
We study ultracold gases of alkali-metal atoms in the quantum degenerate regime. The interatomic interactions in these type of systems can be tuned using resonances induced by magnetic or electric fields. The tunability of the interactions, together with the possibility of confining the atoms with several kinds of external potentials, allows for a completely novel approach to study basic problems in many-body physics, and moreover, allows to enter regimes which have never been accessible in condensed matter or nuclear physics. For example, this has led to the experimental demonstration of an intimate relation between two types of superfluidity: the crossover from Bose-Einstein condensation of tightly bound molecules to the superfluid behavior related to weakly bound BCS-like pairs. Another experimental landmark was reached when the existence of universal Efimov three-body bound states was proven in experiments with ultracold bosonic cesium atoms. In this thesis, we study several aspects of these strongly interacting and ultracold atomic gases. We develop an analytical model that encapsulates all of the relevant scattering physics in atomic systems where open-channel shape resonances and closedchannel Feshbach resonances give rise to complicated and non-trivial scattering properties. This model provides lots of physical insight and is shown to describe important quantities, such as the molecular energies and scattering phase shifts, with a high level of accuracy. The model is compared to full numerical coupled-channel calculations in two atomic systems: rubidium and lithium. We study the BCS-BEC crossover using a many-body description of the ultracold gas that includes the non-trivial energy dependence of the scattering model. We show that it gives rise to superfluid behavior associated with the formation of BCS-like pairs while the low-energy interactions are repulsive in character. The energy dependence of the interactions is crucial, as it gives rise to attractive interactions at the Fermi energy, necessary for the formation of Cooper pairs. We demonstrate new ways of controlling the interatomic interactions using a combination of magnetic and electric fields. This leads to experimental control of, for instance, the three-body parameter in the context of Efimov physics and of non-universal behavior in the BCS-BEC crossover in fermionic gases. Using a four-body method based on first principles, we solve the molecule-molecule scattering problem to calculate several important properties of bosonic and fermionic Summary 145 molecules that consist of light and heavy atoms. These type of molecules are of current experimental interest, and we predict several exciting relations between three- and four-body observables in these type of systems.
We theoretically characterize interactions, energetics, and chemical reaction paths in ionic two-body and three-body systems of alkali-metal and alkaline-earth-metal atoms in the context of modern experiments with cold hybrid ion-atom mixtures. Using ab initio techniques of quantum chemistry such as the coupled-cluster method, we calculate ground-state electronic properties of all diatomic AB+ and most of the triatomic A2B+ molecular ions consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and Yb atoms. Different geometries and wave-function symmetries of the ground state are found for different classes of molecular ions. We analyze intermolecular interactions in the investigated systems including additive two-body and nonadditive three-body ones. As an example we provide two-dimensional interaction potential-energy surfaces for KRb++K and Rb++Sr2 mixtures. We identify possible channels of chemical reactions based on the energetics of the reactants. The present results may be useful for investigating controlled chemical reactions and other applications of molecular ions formed in cold hybrid ion-atom systems.