Long-range interactions in the ozone molecule: spectroscopic and dynamical points of view

Using the multipolar expansion of the electrostatic energy, we have characterized the asymptotic interactions between an oxygen atom O$(^3P)$ and an oxygen molecule O$_2(^3\Sigma_g^-)$, both in their electronic ground state. We have calculated the interaction energy induced by the permanent electric quadrupoles of O and O$_2$ and the van der Waals energy. On one hand we determined the 27 electronic potential energy surfaces including spin-orbit connected to the O$(^3P)$ + O$_2(^3\Sigma_g^-)$ dissociation limit of the O--O$_2$ complex. On the other hand we computed the potential energy curves characterizing the interaction between O$(^3P)$ and a O$_2(^3\Sigma_g^-)$ molecule in its lowest vibrational level and in a low rotational level. Such curves are found adiabatic to a good approximation, namely they are only weakly coupled to each other. These results represent a first step for modeling the spectroscopy of ozone bound levels close to the dissociation limit, as well as the low energy collisions between O and O$_2$ thus complementing the knowledge relevant for the ozone formation mechanism.Comment: Submitted to J. Chem. Phys. after revisio

Formation of ultracold SrYb molecules in an optical lattice by photoassociation spectroscopy: theoretical prospects

State-of-the-art {\em ab initio} techniques have been applied to compute the potential energy curves for the SrYb molecule in the Born-Oppenheimer approximation for the ground state and first fifteen excited singlet and triplet states within the coupled-cluster framework. The leading long-range coefficients describing the dispersion interactions at large interatomic distances are also reported. The electric transition dipole moments have been obtained as the first residue of the polarization propagator computed with the linear response coupled-cluster method restricted to single and double excitations. Spin-orbit coupling matrix elements have been evaluated using the multireference configuration interaction method restricted to single and double excitations with a large active space. The electronic structure data was employed to investigate the possibility of forming deeply bound ultracold SrYb molecules in an optical lattice in a photoassociation experiment using continuous-wave lasers. Photoassociation near the intercombination line transition of atomic strontium into the vibrational levels of the strongly spin-orbit mixed $b^3\Sigma^+$, $a^3\Pi$, $A^1\Pi$, and $C^1\Pi$ states with subsequent efficient stabilization into the $v^{\prime\prime}=1$ vibrational level of the electronic ground state is proposed. Ground state SrYb molecules can be accumulated by making use of collisional decay from $v^{\prime\prime}=1$ to $v^{\prime\prime}=0$. Alternatively, photoassociation and stabilization to $v^{\prime\prime}=0$ can proceed via stimulated Raman adiabatic passage provided that the trapping frequency of the optical lattice is large enough and phase coherence between the pulses can be maintained over at least tens of microseconds

Two-photon coherent control of femtosecond photoassociation

Photoassociation with short laser pulses has been proposed as a technique to create ultracold ground state molecules. A broad-band excitation seems the natural choice to drive the series of excitation and deexcitation steps required to form a molecule in its vibronic ground state from two scattering atoms. First attempts at femtosecond photoassociation were, however, hampered by the requirement to eliminate the atomic excitation leading to trap depletion. On the other hand, molecular levels very close to the atomic transition are to be excited. The broad bandwidth of a femtosecond laser then appears to be rather an obstacle. To overcome the ostensible conflict of driving a narrow transition by a broad-band laser, we suggest a two-photon photoassociation scheme. In the weak-field regime, a spectral phase pattern can be employed to eliminate the atomic line. When the excitation is carried out by more than one photon, different pathways in the field can be interfered constructively or destructively. In the strong-field regime, a temporal phase can be applied to control dynamic Stark shifts. The atomic transition is suppressed by choosing a phase which keeps the levels out of resonance. We derive analytical solutions for atomic two-photon dark states in both the weak-field and strong-field regime. Two-photon excitation may thus pave the way toward coherent control of photoassociation. Ultimately, the success of such a scheme will depend on the details of the excited electronic states and transition dipole moments. We explore the possibility of two-photon femtosecond photoassociation for alkali and alkaline-earth metal dimers and present a detailed study for the example of calcium

Ab initio calculation of the KRb dipole moments

The relativistic configuration interaction valence bond method has been used to calculate permanent and transition electric dipole moments of the KRb heteronuclear molecule as a function of internuclear separation. The permanent dipole moment of the ground state $X^1\Sigma^+$ potential is found to be 0.30(2) $ea_0$ at the equilibrium internuclear separation with excess negative charge on the potassium atom. For the $a^3\Sigma^+$ potential the dipole moment is an order of magnitude smaller (1 $ea_0=8.47835 10^{-30}$ Cm) In addition, we calculate transition dipole moments between the two ground-state and excited-state potentials that dissociate to the K(4s)+Rb(5p) limits. Using this data we propose a way to produce singlet $X^1\Sigma^+$ KRb molecules by a two-photon Raman process starting from an ultracold mixture of doubly spin-polarized ground state K and Rb atoms. This Raman process is only allowed due to relativistic spin-orbit couplings and the absence of gerade/ungerade selection rules in heteronuclear dimers.Comment: 16 pages, 7 figure

Dispersion coefficients of the excited states of lithium atoms

The dispersion coefficients of a number of the low-lying states of Li are determined for the homonuclear case. The Li wave functions and energies were computed in a frozen core Hamiltonian with a semiempirical polarization potential. Besides computing the dispersion coefficients, the scalar and tensor polarizabilities and oscillator strengths are computed and generally seen to be in good agreement with other accurate calculations

Large atom number dual-species magneto-optical trap for fermionic 6Li and 40K atoms

We present the design, implementation and characterization of a dual-species magneto-optical trap (MOT) for fermionic 6Li and 40K atoms with large atom numbers. The MOT simultaneously contains 5.2x10^9 6Li-atoms and 8.0x10^9 40K-atoms, which are continuously loaded by a Zeeman slower for 6Li and a 2D-MOT for 40K. The atom sources induce capture rates of 1.2x10^9 6Li-atoms/s and 1.4x10^9 40K-atoms/s. Trap losses due to light-induced interspecies collisions of ~65% were observed and could be minimized to ~10% by using low magnetic field gradients and low light powers in the repumping light of both atomic species. The described system represents the starting point for the production of a large-atom number quantum degenerate Fermi-Fermi mixture

Ultracold collisions of oxygen molecules

Collision cross sections and rate constants between two ground- state oxygen molecules are investigated theoretically at translational energies below $\sim 1$K and in zero magnetic field. We present calculations for elastic and spin- changing inelastic collision rates for different isotopic combinations of oxygen atoms as a prelude to understanding their collisional stability in ultracold magnetic traps. A numerical analysis has been made in the framework of a rigid- rotor model that accounts fully for the singlet, triplet, and quintet potential energy surfaces in this system. The results offer insights into the effectiveness of evaporative cooling and the properties of molecular Bose- Einstein condensates, as well as estimates of collisional lifetimes in magnetic traps. Specifically, $^{17}O_{2}$ looks like a good candidate for ultracold studies, while $^{16}O_{2}$ is unlikely to survive evaporative cooling. Since $^{17}O_{2}$ is representative of a wide class of molecules that are paramagnetic in their ground state we conclude that many molecules can be successfully magnetically trapped at ultralow temperatures.Comment: 15 pages, 9 figure

Limit on suppression of ionization in metastable neon traps due to long-range anisotropy

This paper investigates the possibility of suppressing the ionization rate in a magnetostatic trap of metastable neon atoms by spin-polarizing the atoms. Suppression of the ionization is critical for the possibility of reaching Bose-Einstein condensation with such atoms. We estimate the relevant long-range interactions for the system, consisting of electric quadrupole-quadrupole and dipole-induced dipole terms, and develop short-range potentials based on the Na_2 singlet and triplet potentials. The auto-ionization widths of the system are also calculated. With these ingredients we calculate the ionization rate for spin-polarized and for spin-isotropic samples, caused by anisotropy of the long-range interactions. We find that spin-polarization may allow for four orders of magnitude suppression of the ionization rate for Ne. The results depend sensitively on a precise knowledge of the interaction potentials, however, pointing out the need for experimental input. The same model gives a suppression ratio close to unity for metastable xenon in accordance with experimental results, due to a much increased anisotropy in this case.Comment: 15 pages including figures, LaTex/RevTex, uses epsfig.st

Theoretical study of the absorption spectra of the lithium dimer

For the lithium dimer we calculate cross sections for absorption of radiation from the vibrational-rotational levels of the ground X [singlet Sigma g +] electronic state to the vibrational levels and continua of the excited A [singlet Sigma u +] and B [singlet Pi u] electronic states. Theoretical and experimental data are used to characterize the molecular properties taking advantage of knowledge recently obtained from photoassociation spectroscopy and ultra-cold atom collision studies. The quantum-mechanical calculations are carried out for temperatures in the range from 1000 to 2000 K and are compared with previous calculations and measurements.Comment: 20 pages, revtex, epsf, 6 fig

Electronic spectral shift of oxygen-filled (6,6) carbon nanotubes

Electronic state modulation of the armchair (6,6) carbon nanotubes filled with a linear assembly of oxygen molecules is addressed theoretically. Ferromagnetic coupling of encapsulated oxygen produces a magnetic field with cylindrical symmetry, which deviates the electron's eigenenergies from those prior to the oxygen absorption. An intriguing spectral gap arises near the Fermi energy, at which the gap formation is allowed only when the tube length equals to a multiple of three in units of carbon hexagon. A possible means to detect the selective gap formation is discussed.Comment: 4 pages, 5 figure