By identifying a special class of atomic negative ion states where all electron spins are unpaired and where the nuclear charge is partially unscreened, we predict, via large-scale state-specific calculations, that and have states which belong to the discrete spectrum even though they are very highly excited and embedded in a multitude of ionization thresholds. For example, the state lies 600.6 eV above the O ground state and yet it is bound. For , the two maximum spin states, and , are connected by an electric dipole transition with and with transition rate . For these unique states, the reliable prediction of the relevant energy differences demanded the execution of systematic all-electron calculations, with inter- and intra-shell correlations included.
The first experimental studies of Os(-) reveal the presence of two very strong resonances. One state is a narrow shape resonance lying only 3.52(12) meV above the ground state detachment threshold, while the other is bound by 11.48(12) meV. Convincing evidence that these states have odd parity is presented, making Os(-) the only known atomic negative ion with bound states of opposite parity. Additionally, the binding energies for the Os(-) ground state ((4)F(e)(9/2)) and first excited state ((4)F(e)(7/2)) are measured to be 1.077 80(12) eV and 0.553(3) eV, respectively.
Atomic anions are generally not amenable to optical spectroscopy because they are loosely bound systems and rarely have bound excited states. Until recently, there was only one known negative ion with a strong bound–bound electronic transition, the osmium anion Os − . The electric-dipole transition between the 4 F e 9/2 ground and 6 D o J excited state of this ion provides unique insight into the structure of atomic anions. In addition, it may enable the preparation of ultracold ensembles of negative ions. Laser excitation of the electric-dipole transition in Os − ions could be used to laser-cool them to microkelvin temperatures. If demonstrated to be successful, the technique would allow the cooling of any species of negatively charged ions - from subatomic particles to molecular anions - to ultracold temperatures by sympathetic cooling. We have been investigating the bound-bound electric-dipole transition in Os − by high-resolution laser spectroscopy with a view to using it for the first laser cooling of negative ions. The principle of the method, its potential applications, as well as experimental results are presented.
The negative ion of lanthanum has one of the richest bound-state spectra observed for an atomic negative ion and it has been proposed as a promising candidate for laser cooling, which has not yet been achieved for any negatively charged system. In the present study, radiative decays of low-lying excited states of ${\mathrm{La}}^{\ensuremath{-}}$ were experimentally investigated at the DESIREE cryogenic electrostatic ion-beam storage ring facility using state-selective photodetachment over storage times of up to 800 s. Independently, the transition rates for the relevant states were calculated using a high-precision hybrid theoretical approach. The measured lifetime of the lowest excited state of ${\mathrm{La}}^{\ensuremath{-}}$
(3F3e) of 132(20) s agrees very well with the theoretical calculations and previous predictions. However, a puzzling discrepancy exists for the next-higher state
3F4e, with the experiments yielding a lifetime $\ensuremath{\sim}4$ times shorter than calculated, highlighting the challenges for this complex ion. The results provide valuable insights into the prospects for laser cooling ${\mathrm{La}}^{\ensuremath{-}}$.
The strong-field-approximation theory of high-order above-threshold ionization of atoms is generalized to include the electron spin. The obtained rescattering amplitude consists of a direct and exchange part. On the examples of excited He atoms as well as
Li+ and
Be++ ions, it is shown that the interference of these two amplitudes leads to an observable difference between the photoelectron momentum distributions corresponding to different initial spin states: Pronounced minima appear for singlet states, which are absent for triplet states.
We show that the recently observed class of long-range ion-Rydberg molecules can be divided into two families of states, which are characterized by their unique electronic structures resulting from the ion-induced admixture of quantum defect-split Rydberg
nP states with different low-field-seeking high-
l states. We predict that in both cases, these diatomic molecular states can bind additional ground-state atoms lying within the orbit of the Rydberg electron, thereby forming charged ultralong-range Rydberg molecules (ULRMs) with binding energies similar to that of conventional nonpolar ULRMs. To demonstrate this, we consider a Rydberg atom interacting with a single ground-state atom and an ion. The additional atom breaks the system's cylindrical symmetry, which leads to mixing between states that would otherwise be decoupled. The electronic structure is obtained using exact diagonalization over a finite basis and the vibrational structure is determined using the multiconfiguration time-dependent Hartree method. Due to the lobelike structure of the electronic density, bound trimers with both linear and nonlinear geometrical configurations of the three nuclei are possible. The predicted trimer binding energies and excitation series are distinct enough from those of the ion-Rydberg dimer to be observed using current experimental techniques.
We establish a new iterative method for computing rigorous lower bounds for the ground-state energies of all atoms and ions. The accuracy of the resulting bounds depends on two ingredients: the quality of the initial energy estimate and the quality of the used upper bound for the maximum number of bound electrons,
Nc(Z), as a function of the nuclear charge
Z>0. In particular, this new method allows us to establish the explicit lower bound
E(N,Z)≥−0.8710N1/3Z2 for the ground-state energy
E(N,Z) of the atom/ion with
N∈N electrons and nuclear charge
Z∈(0,N], thereby considerably improving the best known constant
A=(3/2)1/3≈1.1447 in the estimate
E(N,Z)≥−AN1/3Z2 for
0<Z≤N and coming much closer to the best possible constant given by the Thomas-Fermi asymptotics
limN→∞∣E(N,N)∣N−7/3=−ETF(1)≈0.7687 derived in Adv. Math., 23(1) by Lieb and Simon. To demonstrate the potential and the limits of our method, we also compute explicit lower bounds for the ground-state energies
E(N,N) of all atoms with
2≤N≤86 and we compare them with the bounds obtained in J. Chem. Phys., 62(8) by Hertel, Lieb, Thirring and the bounds obtained by Seco in his dissertation. Finally, we also provide a uniqueness result for the expectation values of the kinetic, potential and interaction energies on the ground-state space.