arXiv subjects

Stefan Willitsch

Publications and source records attributed to Stefan Willitsch.

At least 19 recordsLinked to original sources

arXiv2026

Charge-partition pathways in strong-field photoionization of carbonyl sulfide monomers and dimers

Strong-field photoionization of molecules and molecular clusters gives rise to a rich variety of fragmentation pathways governed by charge localization and redistribution on ultrafast timescales. Here, we report a velocity-map imaging study of the strong-field photoionization and fragmentation of carbonyl sulfide (OCS) monomers and dimers driven by 150 femtosecond (fs) laser pulses at 775~nm. The images of the total kinetic-energy and angular distributions of the OCS$^{2+}$, S$^+$, and CO$^+$ fragments were interpreted with the help of electronic-structure calculations of the potential energy surfaces for OCS$^+$ and OCS$^{2+}$. We identify distinct dissociation pathways of singly and doubly ionized OCS, including two-body breakup channels of OCS$^+$ into $\mathrm{S}^+ + \mathrm{CO}$ and $\mathrm{CO}^+ + \mathrm{S}$, dissociation of OCS$^{2+}$ into $\mathrm{S}^+ + \mathrm{CO}$$^+$ as well as higher-order three-body fragmentation. In addition, the images of the OCS$^{2+}$ channel exhibit near-zero-momentum components, low-energy isotropic features, and highly anisotropic contributions at high kinetic energies that cannot be explained by monomer ionization alone. Analysis of the KER distributions and angular anisotropies indicates that these features originate from the breakup of multiply charged OCS dimers ((OCS)$_2^{2+}$, (OCS)$_2^{3+}$, and (OCS)$_2^{4+}$) through charge-separation channels. Our results illustrate how dynamic signatures of strong-field fragmentation evolve from intramolecular dissociation in isolated molecules to intermolecular charge separation in weakly bound clusters providing a unified picture of charge-driven dissociation dynamics beyond the single-molecule limit.

physics.chem-ph↗

arXiv2026

Full-Dimensional Reactive Potential Energy Surfaces for OCS$^+$ $\rightarrow$ CO+S$^+$ Dissociation: Ground and Excited States

Full-dimensional reactive potential energy surfaces (PESs) for the OCS$^+$ cation are constructed to describe S$^+$ loss in the electronic ground state and seven low-lying electronically excited states. High-level \textit{ab initio} reference energies were computed at the MRCI+Q/aug-cc-pVTZ level and were used to generate PESs employing reproducing kernel Hilbert space representations (RKHS). The PESs accurately reproduce the measured dissociation limits to CO(X$^1\Sigma^+$)+S$^+$ in different electronic states. The topology of the PESs reveals multiple linear and T-shaped minima, pronounced angular anisotropy, and state-crossing manifolds. Exploratory quasi-classical trajectory simulations on selected PESs confirm numerical stability and energy conservation, illustrating the suitability of the surfaces for dynamical applications. The present work represents the most comprehensive characterization to date of the lowest PESs of OCS$^+$ and provides a reliable foundation for future studies of the photodissociation of OCS$^+$ and the chem-ionization dynamics of OCS.

physics.chem-ph↗

arXiv2026

Quantum-logic spectroscopy of forbidden vibrational transitions in single nitrogen molecular ions

Electric-dipole forbidden spectroscopic transitions in atoms form the basis of many advanced implementations of quantum computers, atomic clocks and quantum sensors. Coherently addressing such transitions in molecules which are among the most ubiquitous and versatile quantum objects has remained a long-standing challenge owing to their complex energy-level structure. Here, we report the search, observation and coherent manipulation of electric-quadrupole rotational-vibrational transitions in single trapped molecules using a quantum-logic-spectroscopy protocol. We identified individual hyperfine-Zeeman-rotational components of the fundamental vibrational transition of the nitrogen molecular ion, N$_2^+$, and performed coherent population transfer between energy levels. Our work opens up new perspectives for precision molecular spectroscopy, for high-fidelity qubits encoded in the rotational-vibrational motion of molecules, for precise infrared molecular clocks and for searches for new physics

physics.atom-ph↗

arXiv2025

Automation in quantum logic experiments with cold molecular ions

Modern experiments with cold molecular ions have reached a high degree of complexity requiring frequent sample preparation, state initialization and protocol execution while demanding precise control over multiple devices and laser sources. To maintain a high experimental duty cycle and robust measurement conditions, automation becomes essential. We present a fully automated control system for the preparation of trapped state-selected molecular ions and subsequent quantum logic-based experiments. Adaptive feedback routines based on real-time image analysis introduce and identify single molecular ions in atomic-ion Coulomb crystals. By appropriate manipulation of the trapping potentials, excess atomic ions are released from the trap to produce dual-species two-ion strings, here Ca$^+-$N$_2^+$. After mass and state identification of the molecular ion, nanosecond-level synchronization of laser pulses employing the Sinara/ARTIQ framework and real-time data analysis enable quantum-logic-spectroscopic measurements. The present automated control system enables robust, unsupervised operation over extended periods resulting in an increase of the number of experimentation cycles by about a factor of ten compared to manual operation and a factor of about eight in loaded molecules in typical practical situations. The modular, distributed design of the system provides a scalable blueprint for similar molecular-ion experiments.

physics.atom-ph↗

arXiv2025

Control of chemical reactions in radiofrequency ion traps

Over the past years, radiofrequency ion traps have become an attractive platform for studying chemical reactions as they enable a high degree of control over ion-molecule dynamics. In this review, we summarize techniques for the trapping and cooling of atomic and molecular ions in radiofrequency traps including Doppler and resolved-sideband laser cooling, sympathetic cooling, and cryogenic buffer-gas methods. We discuss strategies for controlling key reaction parameters: the preparation of specific internal quantum states by internal cooling, optical pumping, state-selective photoionization and quantum-logic spectroscopy; the manipulation of collision energies through micromotion control, dynamic trapping and combination with molecular beams; and the selection of molecular structure via isotopic substitution, conformational separation and isomer-specific ion generation. We illustrate applications of these approaches by discussing studies on quantum-state-dependent kinetics, quantum-resonance effects and structure-sensitive reactivity in ion-neutral collisions. We conclude by outlining future challenges, including full state-to-state reaction mapping, reaching the ultracold quantum regime free of micromotion, and the exploration of complex and chiral systems.

physics.chem-ph↗

arXiv2025

Isomer- and state-dependent ion-molecule reactions between Coulomb-crystallised Ca$^+$ ions and 1,2-dichloroethene

We report a systematic investigation of isomer- and state-dependent reactions between Coulomb-crystallised laser-cooled Ca$^+$ ions and \emph{cis/trans}-1,2-dichloroethene (DCE) isomers. By manipulating the electronic state populations of Ca$^+$ through tuning of laser cooling parameters, we observed distinct reactivities in its ground and excited states, as well as with the geometric isomers of DCE. Our experiments revealed two primary reaction channels, formation of CaCl$^+$ and C$_2$HCaCl$^+$, followed by secondary reaction pathways. While excited-state reactions proceed at rate coefficients consistent with capture theory predictions, ground-state reactions show a systematically lower reactivity. \emph{Ab initio} calculations of reaction pathways suggest that this suppression stems from the formation of long-lived reaction complexes. The \textit{cis} isomer was found to exhibit a higher reactivity with all electronic states of Ca$^+$ than its \textit{trans} counterpart. The present study provides insights into the combined effects of molecular structure and quantum states influencing ion-molecule reaction dynamics.

physics.chem-ph↗

arXiv2025

The role of spectator modes in the quantum-logic spectroscopy of single trapped molecular ions

Quantum-logic spectroscopy has become an increasingly important tool for the state detection and readout of trapped atomic and molecular ions which do not possess easily accessible closed-cycling optical transitions. In this approach, the internal state of the target ion is mapped onto a co-trapped auxiliary ion. This mapping is typically mediated by normal modes of motion of the two-ion Coulomb crystal in the trap. The present study investigates the role of spectator modes not directly involved in a measurement protocol relying on a state-dependent optical-dipole force. We identify a Debye-Waller-type effect that modifies the response of the two-ion string to the force. We show that cooling the spectator modes of the string allows for the detection of the rovibrational ground state of an N$_2^+$ molecular ion with a computed statistical fidelity exceeding 99.99%, improving on previous experiments by more than an order of magnitude while also halving the experimental time. This enhanced sensitivity enables the simultaneous identification of multiple rotational states with markedly weaker signals.

physics.atom-ph↗

arXiv2025

Ion counting and temperature determination of Coulomb-crystallized laser-cooled ions in traps using convolutional neural networks

Coulomb crystals -- ordered structures of cold ions confined in ion traps -- find applications in a variety of research fields. The number and temperature of the ions forming the Coulomb crystals are two key attributes of interest in many trapped-ion experiments. Here, we present a fast and accurate approach to determining these attributes from fluorescence images of the ions based on convolutional neural networks (CNNs). In this approach, we first generate a large number of images of Coulomb crystals with different ion numbers and temperatures using molecular-dynamics simulations and then train CNN models on these images to classify the desired attributes. The classification performance of several common pretrained CNN models was compared in example tasks. We find that for crystals with ion numbers in the range 100--299 and secular temperatures of 5--15 mK, the best-performing model can discern number variations on the level of one ion with an accuracy of 93% and temperature variations by 1 mK with an accuracy of 92%. Since the trained model can be directly integrated into experiments, in-situ determination of these attributes can be realized in a non-invasive fashion, which has the potential to greatly facilitate the analysis and control of trapped ions in real time.

physics.atom-ph↗

arXiv2023

Coupling trapped ions to a nanomechanical oscillator

Cold ions in traps are well-established, highly controllable quantum systems with a wide variety of applications in quantum information, precision spectroscopy, clocks and chemistry. Nanomechanical oscillators are used in advanced sensing applications and for exploring the border between classical and quantum physics. Here, we report on the implementation of a hybrid system combining a metallic nanowire with laser-cooled ions in a miniaturised ion trap. We demonstrate resonant and off-resonant coupling of the two systems and the coherent motional excitation of the ion by the mechanical drive of the nanowire. The present results open up avenues for mechanically manipulating the quantum motion of trapped ions, for the development of ion-mechanical hybrid quantum systems and for the sympathetic cooling of mechanical systems by trapped ions and vice versa.

physics.atom-ph↗

arXiv2023

Cold trapped molecular ions and hybrid platforms for ions and neutral particles

We review recent progress in the field of cold trapped molecular ions. A new generation of collision and cold chemistry experiments between atoms and ions has emerged, where cold atoms and ions are brought into contact in a controlled way in novel hybrid atom-ion platforms. Furthermore, new possibilities for the preparation and detection of molecular quantum states with high sensitivity and precision have been demonstrated based on quantum-logic schemes. These advances represent important stepping stones for new directions in fundamental research and technological applications across various domains including precision measurements, quantum technologies and chemical dynamics.

physics.atom-ph↗

arXiv2023

Optimized strategies for the quantum-state preparation of single trapped nitrogen molecular ions

This work examines optimized strategies for the preparation of single molecular ions in well-defined rotational quantum states in an ion trap with the example of the molecular nitrogen ion N2+. It advances a two-step approach consisting of an initial threshold-photoionization stage which produces molecular ions with a high probability in the target state, followed by a measurement-based state purification of the sample. For this purpose, a resonance-enhanced threshold photoionization scheme for producing N2+ in its rovibrational ground state proposed by Gardner et al. [Sci. Rep. 9, 506 (2019)] was characterized. The molecular state was measured using a recently developed quantum-non-demolition state-detection method finding a total fidelity of 38(7)% for producing ground-state N2+ under the present experimental conditions. By discarding ions from the trap not found to be in the target state, essentially state-pure samples of single N2+ ions can be generated for subsequent state-specific experiments.

physics.atom-ph↗

arXiv2023

Experimental implementation of laser cooling of trapped ions in strongly inhomogeneous magnetic fields

We demonstrate the Doppler laser cooling of $^{40}$Ca$^+$ ions confined in a segmented linear Paul trap in the presence of a strong quadrupolar magnetic field generated by two permanent ring magnets. Magnetic field gradients of 800 to 1600 G/mm give rise to a highly position-dependent Zeeman shift on the energy levels of the trapped ions. Efficient laser cooling is demonstrated using two 397 nm cooling laser beams with appropriate wavelengths and polarizations and one 866 nm repumper laser beam. Coulomb crystals of ions are found to exhibit similar secular temperatures to those trapped in absence of the magnetic field. In addition, the position dependency of the Zeeman effect is used to generate a map of the field strength. This work forms the basis for developing hybrid trapping experiments for cold ions and neutral molecules that consist of an ion and a magnetic trap to study cold interactions between these species, and opens up new possibilities for quantum-science experiments that employ trapped ions in inhomogeneous magnetic fields.

physics.atom-ph↗

arXiv2023

Trapping and sympathetic cooling of conformationally selected molecular ions

We report the generation, trapping and sympathetic cooling of individual conformers of molecular ions with the example of cis- and trans-meta-aminostyrene. Following conformationally selective photoionization, the incorporation of the conformers into a Coulomb crystal of laser-cooled calcium ions was confirmed by fluorescence imaging, mass spectrometry and molecular dynamics simulations. We deduce the molecules to be stable in the trap environment for more than ten minutes. The present results pave the way for the spectroscopy and controlled chemistry of distinct ionic conformers in traps.

physics.chem-ph↗

arXiv2023

Charge transfer of polyatomic molecules in ion-atom hybrid traps: Stereodynamics in the millikelvin regime

Rate constants for the charge transfer reaction between N${}_{2}$H${}^{+}$ and Rb in the mK regime are measured in an ion-atom hybrid trap and are found to be lower than the Langevin capture limit. Multireference ab initio computation of the potential energy surfaces involved in the reaction reveals that the low-temperature charge transfer is hindered by short-range features highly dependent on the collision angle and is promoted by a deformation of the molecular frame. The present study highlights the importance of polyatomic effects and of stereodynamics in cold molecular ion-neutral collisions.

physics.atom-ph↗

arXiv2023

Conformational and state-specific effects in reactions of 2,3-dibromobutadiene with Coulomb-crystallized calcium ions

Recent advances in experimental methodology enabled studies of the quantum-state and conformational dependence of chemical reactions under precisely controlled conditions in the gas phase. Here, we generated samples of selected gauche and s-trans 2,3-dibromobutadiene (DBB) by electrostatic deflection in a molecular beam and studied their reaction with Coulomb crystals of laser-cooled $\mathrm{Ca^{+}}$ ions in an ion trap. The rate coefficients for the total reaction were found to strongly depend on both the conformation of DBB and the electronic state of $\mathrm{Ca^{+}}$. In the $\mathrm{(4p)~^{2}P_{1/2}}$ and $\mathrm{(3d)~^{2}D_{3/2}}$ excited states of $\mathrm{Ca^{+}}$, the reaction is capture-limited and faster for the gauche conformer due to long-range ion-dipole interactions. In the $\mathrm{(4s)~^{2}S_{1/2}}$ ground state of $\mathrm{Ca^{+}}$, the reaction rate for s-trans DBB still conforms with the capture limit, while that for gauche DBB is strongly suppressed. The experimental observations were analysed with the help of adiabatic capture theory, ab-initio calculations and reactive molecular dynamics simulations on a machine-learned full-dimensional potential energy surface of the system. The theory yields near-quantitative agreement for s-trans-DBB, but overestimates the reactivity of the gauche-conformer compared to the experiment. The present study points to the important role of molecular geometry even in strongly reactive exothermic systems and illustrates striking differences in the reactivity of individual conformers in gas-phase ion-molecule reactions.

physics.chem-ph↗

arXiv2022

Laser Cooling of Trapped Ions in Strongly Inhomogeneous Magnetic Fields

Hybrid traps for the simultaneous confinement of neutrals and ions have recently emerged as versatile tools for studying interactions between these species at very low temperatures. Such traps rely on the combination of different types of external fields for the confinement of either species raising the question of interactions between the individual traps. Here, the influence of a strongly inhomogeneous magnetic field used for trapping neutrals on the trapping and laser cooling of a single Ca$^+$ ion in a radiofrequency ion trap is studied theoretically using molecular-dynamics simulations based on multilevel rate equations. The inhomogeneous magnetic field couples the different components of the ion motion and introduces position-dependent Zeeman splittings. Nonetheless, laser cooling is still found to work efficiently as the ion samples different magnetic field strengths and directions along its trajectory. Offsetting the centres of the two traps generates a linear magnetic-field gradient so that multiple lasers are required to address the resulting range of Zeeman splittings in order to ensure efficient cooling. The present study yields detailed insights into the ion cooling dynamics in combined magnetic and radiofrequency electric fields relevant for the characterisation and optimisation of hybrid trapping experiments.

physics.atom-ph↗

arXiv2022

Ion loss events in a cold Rb-Ca$^+$ hybrid trap: photodissociation, black-body radiation and non-radiative charge exchange

We theoretically investigate the collisional dynamics of laser-cooled $^{87}$Rb ground-state atoms and $^{40}$Ca$^+$ ground-state ions in the context of the hybrid trap experiment of Ref. [Phys. Rev. Lett. 107, 243202 (2011)], leading to ion losses. Cold $^{87}$Rb$^{40}$Ca$^+$ ground-state molecular ions are created by radiative association, and we demonstrate that they are protected against photodissociation by black-body radiation and by the $^{40}$Ca$^+$ cooling laser at 397~nm. This study yields an interpretation of the direct observation of $^{87}$Rb$^{40}$Ca$^+$ ions in the experiment, in contrast to other hybrid trap experiments using other species. Based on novel molecular data for the spin-orbit interaction, we also confirm that the non-radiative charge-exchange is the dominant loss process for Ca$^+$ and obtain rates in agreement with experimental observations and a previous calculation.

physics.chem-ph↗

arXiv2022

Frequency stabilisation and SI tracing of mid-infrared quantum-cascade lasers for precision molecular spectroscopy

The advancement of technologies for the precise interrogation of molecules offers exciting possibilities for new studies in the realms of precision spectroscopy and quantum technologies. Experiments in these domains often address molecular vibrations in the mid-infrared (MIR) spectral region, thus generating the need for spectrally pure and accurate MIR laser sources. Quantum-cascade lasers (QCLs) have emerged as flexible sources of coherent radiation available over a wide range of MIR frequencies. Here, we demonstrate a robust approach for the simultaneous linewidth narrowing, frequency stabilisation, and absolute frequency referencing of MIR QCLs all of which are prerequisites for precise spectroscopic experiments. Following upconversion of its radiation to the visible domain, we implement a phase lock of the QCL to a linewidth-narrowed optical frequency comb which is referenced to a remote SI-traceable primary frequency standard via a fibre link for absolute frequency calibration. To achieve a reliable frequency counting of the beat note between the QCL and the OFC, we employ redundant tracking oscillators and demonstrate a frequency instability of $5\times10^{-13}$ at 1 s and $2\times10^{-14}$ at 1000 s integration time, limited by the accuracy of our remote reference.

physics.optics↗