Anisotropy induced Feshbach resonances in a quantum dipolar gas of magnetic atoms

We explore the anisotropic nature of Feshbach resonances in the collision between ultracold magnetic submerged-shell dysprosium atoms, which can only occur due to couplings to rotating bound states. This is in contrast to well-studied alkali-metal atom collisions, where most Feshbach resonances are hyperfine induced and due to rotation-less bound states. Our novel first-principle coupled-channel calculation of the collisions between open-4f-shell spin-polarized bosonic dysprosium reveals a striking correlation between the anisotropy due to magnetic dipole-dipole and electrostatic interactions and the Feshbach spectrum as a function of an external magnetic field. Over a 20 mT magnetic field range we predict about a dozen Feshbach resonances and show that the resonance locations are exquisitely sensitive to the dysprosium isotope.Comment: 5 pages, 4 figure

Electronic structure and spectroscopy of O2 and O2+

We carried out a comprehensive SCF MRD--CI ab initio study of the electronic structure of O$_2$ and O$_2^+$. Potential energy curves (PECs) of about 150 electronic states of O$_2$ and about 100 of O$_2^+$, as well as a number of states of O$_2^{++}$ were computed. The cc--pVQZ basis set augmented with diffuse functions was employed. Spectroscopic parameters ($T_e, T_v, \omega_e, \omega_ex_e, B_e,$ $D_e, D_0$, $\mu$, IP, etc.) are reported. A preliminary sample of the results will be presented. The electronic absorption spectrum of O$_2$ has proved difficult to analyze/interpret due to the unusually large number of electronic states which arise from the peculiar open--shell structure of both the oxygen atomic fragments and the O$_2$ molecule. For instance, there are 62 valence molecular electronic states which correlate to the six lowest dissociation limits resulting from the three valence O atom fragment states ($^3$P, $^1$D, $^1$S). In addition, there are several $nl\lambda$ Rydberg series converging to the X$^2\Pi_g$ ground ionic state and to the lowest two excited states of the cation, a$^4\Pi_u$$_i$ and A$^2\Pi_u$. Furthermore, a number of interactions of various types among several electronic states result in rovibronic perturbations which manifest themselves, e.g., as irregular vibronic structure, hence severely complicating the assignment of the absorption features and the analysis and interpretation of the spectrum. An overview of the electronic states and spectroscopy of O$_2$ will be presented. A chief motivation of this study of O$_2$ was to try to provide a theoretical insight on the nature, energetic position, shape, and dissociation asymptotes, of electronic states located in the 4 eV energy region encompassed between the O$_2^+$ ground state X$^2\Pi_g$ (IP$=12.07$ eV) and the first excited state of the cation a$^4\Pi_u$$_i$ (IP$=16.10$ eV). This in order to aid in the interpretation of experimental data related to the mechanism(s) of the neutral dissociation of the O$_2^{**}$ (Rydberg) superexcited states, which competes with autoionization. We are currently striving to compute PECs of relatively highly excited states of O$_2$ located in the 12--16 eV energy region which might help to visualize possible pathways for the neutral XUV photodissociation of the I, I$^{\prime}$ and I$^{\prime\prime}$ $^3\Pi_u$ superexcited states of O$_2$ leading to the O($^3$P) + O$^{*}$($^3$S, $^5$S) dissociation limits.Ope

Zero kinetic energy-pulsed field ionization and resonance enhanced multiphoton ionization photoelectron spectroscopy: Ionization dynamics of Rydberg states in HBr

The results of rotationally resolved resonance enhanced multiphoton ionization photoelectron spectroscopy and zero kinetic energy‐pulsed field ionization studies on HBr via various rotational levels of the F^ 1Δ_2 and f^ 3Δ_2 Rydberg states are reported. These studies lead to an accurate determination of the lowest ionization threshold as 94 098.9±1 cm^(−1). Observed rotational and spin–orbit branching ratios are compared to the results of ab initio calculations. The differences between theory and experiment highlight the dominant role of rotational and spin–orbit interactions for the dynamic properties of the high‐n Rydberg states involved in the pulsed field ionization process

Laser-induced fluorescence studies of HfF+ produced by autoionization

Autoionization of Rydberg states of HfF, prepared using the optical-optical double resonance (OODR) technique, holds promise to create HfF+ in a particular Zeeman level of a rovibronic state for an electron electric dipole moment (eEDM) 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 (LIF) 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+> state and present a simplified model describing autoionization from a given Rydberg state that assumes no angular dynamics.Comment: 8 pages, 5 figure

Hyperfine, rotational and Zeeman structure of the lowest vibrational levels of the 87^{87}Rb2_2 \tripletex state

We present the results of an experimental and theoretical study of the electronically excited \tripletex state of $^{87}$Rb$_2$ molecules. The vibrational energies are measured for deeply bound states from the bottom up to $v'=15$ using laser spectroscopy of ultracold Rb$_2$ Feshbach molecules. The spectrum of each vibrational state is dominated by a 47\,GHz splitting into a \cog and \clg component caused mainly by a strong second order spin-orbit interaction. Our spectroscopy fully resolves the rotational, hyperfine, and Zeeman structure of the spectrum. We are able to describe to first order this structure using a simplified effective Hamiltonian.Comment: 10 pages, 7 figures, 2 table

Relations between Rydberg-valence interactions in the O₂ molecule

Using a single-configuration formulation, analytical expressions are derived for the (X²Πg) nsσg, npπu, and npσu Rydberg-valence interaction matrix elements in O₂. In addition, new results from diabatic, coupled-channel deperturbations of experimental data dependent on these interactions are reported for n=3 and 4. Using these results, the large differences in magnitude between the Rydberg-valence couplings for the constituent states of the npπuRydberg complex that are predicted by the analytical expressions are verified experimentally. Effective values for several two-electron integrals are obtained semiempirically through comparison between analytical expressions and deperturbed experimental values for the Rydberg-state energies and Rydberg-valence couplings, allowing predictions to be made for the spectroscopy of the npπu ¹Σ−uRydberg states which have yet to be observed

Marked influence of the nature of chemical bond on CP-violating signature in molecular ions HBr+\mathrm{HBr}^{+} and HI+\mathrm{HI}^{+}

Heavy polar molecules offer a great sensitivity to the electron Electric Dipole Moment(EDM). To guide emerging searches for EDMs with molecular ions, we estimate the EDM-induced energy corrections for hydrogen halide ions $\mathrm{HBr}^{+}$ and $\mathrm{HI}^{+}$ in their respective ground $X ^2\Pi_{3/2}$ states. We find that the energy corrections due to EDM for the two ions differ by an unexpectedly large factor of fifteen. We demonstrate that a major part of this enhancement is due to a dissimilarity in the nature of the chemical bond for the two ions: the bond that is nearly of ionic character in $\mathrm{HBr}^{+}$ exhibits predominantly covalent nature in $\mathrm{HI}^{+}$. We conclude that because of this enhancement the HI$^+$ ion may be a potentially competitive candidate for the EDM search.Comment: This manuscript has been accepted for publication in Physical Review Letters. The paper is now being prepared for publicatio

Influence of autoionisation and predissociation on the photoelectron parameters in HBr

Lefebvre-Brion H, Salzmann M, Klausing H-W, Müller M, Böwering N, Heinzmann U. Influence of autoionisation and predissociation on the photoelectron parameters in HBr. Journal of Physics B: Atomic, Molecular and Optical Physics. 1989;22(23):3891-3900

Spin–orbit autoionization and intensities in the double-resonant delayed pulsed-field threshold photoionization of HCl

State‐selected delayed pulsed‐field threshold photoionizationspectra of HCl and DCl are recorded in double‐resonant transitions through the F ^1Δ, E ^1Σ^+, and g ^3Σ^− states of the 4pπ Rydberg configuration. Comparison of observed rotational line strengths with calculated spectra, as well as with available time‐of‐flight photoelectron spectra, provides useful insight on the influence of spin–orbit and rotational autoionization on delayed pulsed‐field threshold photoionization of HCl. Spin–orbit and rotational autoionization are seen to dramatically reduce the ion rotational intensity associated with the upper spin–orbit level of the ion