The usual simplified view of Rydberg states of molecules as consisting of a single Rydberg electron loosely bound to a molecular ion core in a well-defined rotation-vibration state suggests an attractive possibility for state-selective production of molecular ions. A Rydberg electron excited above the energy of the ground state of the ion core will spontaneously autoionize, leaving behind a molecular ion. The autoionizing states are of strongly mixed character due to the ubiquitous nonadiabatic interactions between Rydberg series associated with different states of the ion core. Using our complete Multichannel Quantum Defect Theory (MQDT) fit model for CaF, we have predicted the locations and strengths of special autoionizing resonances that decay into a single rotation-vibration state of a molecular ion. Few molecules are as well characterized as CaF, nor as elegantly simple. We additionally describe the use of core nonpenetrating states as a general method to produce an ensemble of molecular ions in a single, selectable quantum state.
The usual simplified view of Rydberg states of molecules as consisting of a single Rydberg electron loosely bound to a molecular ion core in a well-defined rotation-vibration state suggests an attractive possibility for state-selective production of molecular ions. A Rydberg electron excited above the energy of the ground state of the ion core will spontaneously autoionize, leaving behind a molecular ion. The autoionizing states are of strongly mixed character due to the ubiquitous nonadiabatic interactions between Rydberg series associated with different states of the ion core. Using our complete Multichannel Quantum Defect Theory (MQDT) fit model for CaF, we have predicted the locations and strengths of special autoionizing resonances that decay into a single rotation-vibration state of a molecular ion. Few molecules are as well characterized as CaF, nor as elegantly simple. We additionally describe the use of core nonpenetrating states as a general method to produce an ensemble of molecular ions in a single, selectable quantum state.
"Core nonpenetrating Rydberg states of molecules are a neglected state of matter. They could have a variety of uses, notably state-selective production of molecular ions. Due to the \textit{l}(\textit{l}+1)/r2 centrifugal barrier that prevents the Rydberg electron in high-\textit{l} states from penetrating inside of the ion core, the electron is essentially uncoupled from the ion core, and the system becomes atom-like with long lifetimes, an ""almost good"" \textit{l} quantum number, and electronic transitions that follow ΔJ+=0 and Δv+=0 propensity rules. However, in most molecules access to these states, via a sequence of Δ\textit{l}=+1 transitions from low-n*, low-\textit{l} states, is blocked by the necessity to traverse the ""zone of death,"" in which nonradiative decay mechanisms are prohibitively fast. We exploit Chirped Pulse millimeter-Wave (CPmmW) spectroscopy to efficiently excite Ca atoms and BaF molecules to core nonpenetrating states in the absence of nonradiative decay mechanisms. A universal method for preparing core nonpenetrating Rydberg states of molecules, which combines CPmmW spectroscopy with STImulated Raman Adiabatic Passage (STIRAP), will be discussed."
Abstract Recently, a new method has been introduced to study ion-molecule reactions at very low collision energies, down to below k B ⋅ 1 K (Allmendinger et al 2016 ChemPhysChem 17 3596). To eliminate the acceleration of the ions by stray electric fields in the reaction volume, the reactions are observed within the orbit of a Rydberg electron with large principal quantum number n > 20. This electron is assumed not to influence the reaction taking place between the ion core and the neutral molecules. This assumption is tested here with the example of the He(n) + CO → C(n′) + O + He reaction, which is expected to be equivalent to the He+ + CO → C+ + O + He reaction, using a merged-beam approach enabling measurements of relative reaction rates for collision energies E coll in the range from 0 to about k B ⋅ 25 K with a collision-energy resolution of ∼k B ⋅ 200 mK at E coll = 0. In contrast to the other ion-molecule reactions studied so far with this method, the atomic ion product (C+) is in its electronic ground state and does not have rotational and vibrational degrees of freedom so that the corresponding Rydberg product [C(n′)] cannot decay by autoionization. Consequently, one can investigate whether the principal quantum number is effectively conserved, as would be expected in the spectator Rydberg-electron model. We measure the distribution of principal quantum numbers of the reactant He(n) and product C(n′) Rydberg atoms by pulsed-field ionization following initial preparation of He(n) in states with n values between 30 and 45 and observe that the principal quantum number of the Rydberg electron is conserved during the reaction. This observation indicates that the Rydberg electron is not affected by the reaction, from which we can conclude that it does not affect the reaction either. This conclusion is strengthened by measurements of the collision-energy-dependent reaction yields at n = 30, 35 and 40, which exhibit the same behavior, i.e. a marked decrease below E coll ≈ k B ⋅ 5 K.
We present theoretical and experimental progress towards a new approach for the precision spectroscopy, coherent manipulation and state-to-state chemistry of single isolated molecular ions in the gas phase. Our method uses a molecular beam for creating packets of rotationally cold neutrals from which a single molecule is state-selectively ionized and trapped inside a radiofrequency ion trap. In addition to the molecular ion, a single co-trapped atomic ion is used to cool the molecular external degrees of freedom to the ground state of the trap and to detect the molecular state using state-selective coherent motional excitation from a modulated optical-dipole force acting on the molecule. We present a detailed discussion and theoretical characterization of the present approach. We simulate the molecular signal experimentally using a single atomic ion, indicating that different rovibronic molecular states can be resolved and individually detected with our method. The present approach for the coherent control and non-destructive detection of the quantum state of a single molecular ion opens up new perspectives for precision spectroscopies relevant for, e.g., tests of fundamental physical theories and the development of new types of clocks based on molecular vibrational transitions. It will also enable the observation and control of chemical reactions of single particles on the quantum level. While focusing on N2+ as a prototypical example in the present work, our method is applicable to a wide range of diatomic and polyatomic molecules.
We have studied the nu=1 Rydberg states of BaF in the energy region E=38800-39100 wn (n*=15-25) via optical-optical double resonance spectroscopy. Rydberg states excited above the first ionization potential spontaneously autoionize and 138Ba19F+ ions are detected by TOF-MS. In addition, BaF possesses a particularly low ionization potential, which allows for the study of autoionization dynamics in the absence of predissociative decay. This work extends the assignments of core-penetrating Rydberg states of BaF (Jakubek and Field, 2000) for applications to state-selective ion production schemes. Polarization and Stark spectroscopy techniques will be discussed in the context of accurate and efficient assignment of spectra.
Several diatomic transition metal oxides, rare-earth metal oxides, and fluorides have the unusual property that their bond dissociation energy is larger than their ionization energy. In these molecules, bound levels above the ionization energy can be populated via strong, resonant transitions from the ground state. The only relevant decay channel of these levels is autoionization; predissociation is energetically not possible and radiative decay is many orders of magnitude slower. Starting from translationally cold neutral molecules, translationally cold molecular ions can thus be produced with very high efficiency. By populating bound levels just above the ionization energy, internally cold molecular ions, exclusively occupying the lowest rotational level, are produced. This is experimentally shown here for the dysprosium monoxide molecule DyO, for which the lowest bond dissociation energy is determined to be 0.0831(6) eV above the ionization energy.
Preparing molecules at rest and in a very pure quantum state is a long-standing aspiration in chemistry and physics, so far achieved only for a select set of molecules in dedicated experimental setups. Here, a quantum-limited combination of mass spectrometry and Raman spectroscopy is proposed that should be applicable to a wide range of molecular ions. Excitation of electrons in the molecule followed by uncontrolled decay and branching into several lower-energy states is avoided. Instead, the molecule is always confined to rotational states within the electronic and vibrational ground-state manifold, while a co-trapped atomic ion provides efficient entropy removal and allows for extraction of information about the molecule. The outlined techniques might enable the preparation, manipulation and measurement of a multitude of molecular ion species with the same instrument, with applications including, but not limited to, precise determination of molecular properties and fundamental tests of physics.