Cryogenic Trap Research Articles

High Resolution Rovibrational Spectroscopy of the ν6 and ν3 + ν7 Bands of H2CCCH.

The molecular ion H2CCCH+ has been further investigated in a 4 K cryogenic ion trap instrument employing the leak-out spectroscopy (LOS) method. Transitions within two perpendicular bands, the fundamental ν6 (antisymmetric H-C-H stretch) and the combination band ν3 + ν7 (C≡C stretch and CH2 rock), have been measured in high resolution for the first time. The spectral analysis was aided by high level quantum chemical calculations and by our previous study of the parallel ν1 and ν3 + ν5 bands [Silva, W. G. D. P. ; Mol. Phys. 2023, e2296613]. The novel results presented here have allowed for a seventy-fold improvement on the accuracy of the value of the A0 rotational constant of this near-prolate asymmetric top.

A high-resolution photoelectron spectroscopic and computational study of TaX− (X = C, N, O)

We report on the high-resolution photoelectron spectroscopy of diatomic molecules TaX− (X = C, N, O) anions using a cryogenic ion trap combined with the slow electron velocity imaging (cryo-SEVI) method. We determined the electron affinities of TaC, TaN, and TaO to be 2.098(2), 1.576(2), and 1.069(2) eV, respectively. In addition, the electron affinities of TaX molecules were calculated using the CCSD(T) method with the complete basis sets. To interpret the complicated photoelectron spectra, we predicted the excited states of TaX molecules using the MRCI + Q method, accounting for the spin–orbit coupling effects. Several new excited states of these molecules were observed.

IR and UV Spectroscopy of Gas-Phase Monohydrated Protonated Guanine.

We use UV and infrared photodissociation spectroscopy to study monohydrated protonated guanine in a dual cryogenic ion trap spectrometer. The monohydrated complexes are formed through helium-mediated collisions between bare electrosprayed protonated guanine and low-pressure water vapor in a clustering trap maintained at 180 K, before being transferred to a quadrupole ion trap at 10 K. The spectrum of the monohydrated complex exhibits sharp vibronic transitions at the band origin and becomes broader and higher in intensity further in blue, which is very similar to protonated guanine but with a notable blue shift of ∼1850 cm-1 (∼0.23 eV). The UV hole-burning experiments showed that the vibronic bands recorded in the region of the band origin belong to a single conformer under our experimental conditions. The IR photodissociation spectrum in the 3000-3600 cm-1 range, with the aid of theoretical calculations (SCS-CC2/aug-cc-pVDZ), allowed us to assign the structure to the lowest energy N7-O conformer.

Resolved-sideband cooling of a single Be+9 ion in a cryogenic multi-Penning-trap for discrete symmetry tests with (anti-)protons

Manipulating the motion of individual trapped ions at the single quantum level has become standard practice in radio-frequency ion traps, enabling sweeping advances in quantum information processing and precision metrology. The key step for motional-state engineering is ground-state cooling. Full motional control also bears great potential to explore another regime of sensitivities for fundamental physics tests in Penning traps. Here we demonstrate the key enabling step by implementing resolved-sideband cooling on the axial mode of a single Be+9 ion in a 5 Tesla cryogenic Penning trap. The system has been developed for the implementation of high-precision antimatter experiments to test the fundamental symmetries of the standard model with the highest accuracy in the baryonic sector. We measure an axial phonon number of n¯z=0.10(4) after cooling and demonstrate that the axial heating rate in our system is compatible with the implementation of quantum logic spectroscopy of (anti-)protons. Published by the American Physical Society 2024

Demonstration of Capture, Cooling, Tagging, and Spectroscopic Characterization of UV Photoproduct Ions in a Cryogenic Ion Trap: Application to 266 nm Photofragment Ions from Rhodamine 6G.

We demonstrate a method to determine the structures of the primary photodissociation products from a cryogenically cooled parent ion. In this approach, a target ion is cooled by a pulse of buffer gas and tagged in a 20 K Paul trap. The cold ion is then photodissociated by pulsed (∼5 ns) UV laser excitation, and the ionic products are trapped, cooled, and tagged by introduction of a second buffer gas pulse in the same trap. The tagged fragments are then ejected into a triple focusing, UV/vis/IR time-of-flight photofragmentation mass spectrometer which yields vibrational and electronic spectra of the mass-selected photofragments. These methods are demonstrated by application to the 266 nm photodissociation of the Rhodamine 6G cation to yield the R575 fragment ion based on loss of ethene as well as to a weaker secondary fragment arising from loss of m/z 43.

Electronic and vibrational spectroscopy of benzonitrile cation for astrochemical consideration.

The electronic and vibrational spectra of benzonitrile cation, C6H5CN+ (BZN+), in the gas phase at low temperatures are reported. Measurements were carried out using a cryogenic ion trapping apparatus. The mid-infrared spectrum shows a strong CN stretch at 2130 ± 1 cm-1 (4.694 ± 0.002 µm). The electronic spectrum is reported in the range 5040-5750Å. This covers the forbidden B2B2 ← X2B1 and allowed C2B1 ← X2B1 transitions. The spectrum is dominated by a broad absorption feature at wavelengths shorter than 5250Å, with the strongest absorption located at 5140Å. Experimental data are complemented with quantum chemical calculations carried out at the density functional theory and extended multi-configurational quasi-degenerate perturbation theory level. The spectroscopic results are discussed in the context of astronomical observations in the infrared and visible.

Cryogenic Ion Vibrational Spectroscopy of Protonated Valine: Messenger Tag Effects.

We report the infrared photodissociation spectrum of tagged protonated valine in the range 1000-1900 cm-1, prepared in a cryogenic ion trap. Comparison of experimental results with calculated infrared spectra based on density functional theory shows that the hydroxyl group of the carboxylic acid functionality and the protonated amine group adopt a trans configuration. Nitrogen and methane molecules were used as messenger tags with optimal tagging temperatures of 30 K for N2 and 60 K for CH4. While the calculated infrared spectra of the tagged ion suggest only a weak influence of the messenger tag on the frequency positions of ValH+, the measured intensities for N2-tagged ValH+ appear strongly suppressed for all but the highest frequency feature at 1773 cm-1. We trace this behavior to the binding energy of the N2 tag, which is significantly higher than that of CH4, based on density functional and coupled cluster calculations and rate estimates for photoinduced unimolecular dissociation from statistical theory.

Image-Current Mediated Sympathetic Laser Cooling of a Single Proton in a Penning Trap Down to 170mK Axial Temperature.

We demonstrate a new temperature record for image-current mediated sympathetic cooling of a single proton in a cryogenic Penning trap by laser-cooled ^{9}Be^{+}. An axial mode temperature of 170mK is reached, which is a 15-fold improvement compared to the previous best value. Our cooling technique is applicable to any charged particle, so that the measurements presented here constitute a milestone toward the next generation of high-precision Penning-trap measurements with exotic particles.

Conformation-Selective Ultraviolet-Ultraviolet Hole Burning Spectra of Ubiquitin Ions in a Cryogenic Ion Trap.

Understanding the structural variations of conformational isomers in proteins is crucial for elucidating protein folding mechanisms. Here, we present a novel method for obtaining conformation-selective ultraviolet (UV)-UV hole burning (HB) spectra of ubiquitin ions ((Ubi+zH)+z, z = 7-10) produced via electrospray ionization. Our approach involves binding multiple N2 molecules to ubiquitin ions ((Ubi+zH)+z(N2)m, m = 1-55) within a cryogenic ion trap. Upon exposure to UV irradiation, efficient fragmentation of (Ubi+zH)+z(N2)m occurs, primarily yielding bare (Ubi+zH)+z ions as fragments. The significant mass difference between the parent and fragment ions facilitates the acquisition of UV-UV HB spectra, which reveal the presence of at least two distinct conformers. Molecular dynamics simulations suggest that these conformers correspond to A-state structures, differing only in the interactions of a tyrosine residue with neighboring residues. Our findings underscore UV-UV HB spectroscopy of protein ions as a powerful tool for exploring diverse protein isomers.

Robust and fast microwave-driven quantum logic for trapped-ion qubits

Microwave-driven logic is a promising alternative to laser control in scaling trapped-ion based quantum processors. We implement Mølmer-Sørensen two-qubit gates on 43Ca+ hyperfine clock qubits in a cryogenic (≈25 K) surface trap, driven by near-field microwaves. We achieve gate durations of 154 µs [with 1.0(2)% error] and 331 µs [0.5(1)% error], which approaches the performance of typical laser-driven gates. In the 331 µs gate, we demonstrate a Walsh-modulated dynamical decoupling scheme which suppresses errors due to fluctuations in the qubit frequency as well as imperfections in the decoupling drive itself. Published by the American Physical Society 2024

The Gas Phase Protonation Sites of Six Naturally Occurring Nicotinoids.

The gas phase protonation sites of six naturally occurring nicotinoids, namely nicotine (NIC), nornicotine (NOR), anabasine (ANB), anatabine (ANT), cotinine (COT), and myosmine (MYO), consisting of a common Pyridine and differing non-Pyridine rings, have been determined for the first time at the physiological temperature from cryogenic ion trap infrared spectroscopy and electronic structure calculations. The protonation site on either of these two rings is related to the nicotinoid's biological activity. At room temperature, NIC is a mixture of Pyridine and Pyrrolidine (non-Pyridine) protomers, whereas NOR, ANB, ANT, and COT are pure Pyridine protomers and finally MYO is mostly a Pyroline (non-Pyridine) protomer. The nearly planar structure of MYO-H+, induced by the presence of a conjugated π system and confirmed from calculations and the UV absorption spectra, breaks from the trends observed for NIC, NOR, and ANB, since its structure is drastically different from the structures of the other nicotinoids.

Simulations of a cryogenic, buffer-gas filled Paul trap for low-emittance ion bunches

Many experiments with pulsed ion beams benefit from or even require ion bunches with both small temporal width as well as small energy spread. To achieve optimal ion-beam preparation, a buffer-gas filled cryogenic Paul trap is being developed in the context of the Multi Ion Reflection Apparatus for Collinear Laser Spectroscopy (MIRACLS). There, ion bunches of short-lived radionuclides are trapped in a Multi-Reflection Time-of-Flight (MR-ToF) device. Thus, the ions can be repeatedly probed by a laser beam compared to only once in conventional, single-passage collinear laser spectroscopy. To fulfill MIRACLS’ opposing requirements of a small temporal ion-bunch width and small energy spread, a buffer-gas filled cryogenic Paul trap is envisioned. Ion-optical simulations confirm the advantages of cryogenic temperatures and the linear scaling of the beam emittance as a function of the buffer-gas temperature. Beyond MIRACLS, high-quality ion beams from a cryogenic Paul trap will be beneficial for other precision experiments at radioactive ion beam facilities.

Photodetachment and Tunneling Dissociation of Cryogenic Double-Rydberg Anions NH4.

The Rydberg radical NH4 and the double Rydberg anion (DRA) NH4- have long aroused researchers' interests due to their potential for exploring the reaction dynamics of the H + NH3 → H2 + NH2 reaction, a prototypical penta-atomic system. In this study, we present high-resolution photodetachment spectroscopy of DRA NH4- and ion-molecule complex H-(NH3). We observed multiple new photodetachment channels of DRA NH4-. The energy level of the excited state (3p 2T2) of the Rydberg radical NH4 was determined to be 15052(94) cm-1, in excellent agreement with the principal Schüler band (15061.61 cm-1). Additionally, we observed the tunneling dissociation of NH4- in a cryogenic ion trap with its dissociation lifetime determined to be 19(2) ms.

Off-resonance electronic detection and cooling of ions in a Penning trap

We present a non-destructive electronic detector for stored charged particles in a Penning trap that uses a symmetric electrode arrangement for signal pickup and a resonator without tap. This system has advantageous off-resonance features which are demonstrated by means of detection and cooling measurements with highly charged ions in a cryogenic Penning trap. In particular, it allows for particle detection across a wide range of frequencies that is not concomitant with cooling and offers a novel way to tune a trap with the help of non-destructive measurements on large particle ensembles.

Online-Monitoring of the Enantiomeric Ratio in Microfluidic Chip Reactors Using Chiral Selector Ion Vibrational Spectroscopy.

A novel experimental approach for the rapid online monitoring of the enantiomeric ratio of chiral analytes in solution is presented. The charged analyte is transferred to the gas phase by electrospray. Diastereomeric complexes are formed with a volatile chiral selector in a buffer-gas-filled ion guide held at room temperature, mass-selected, and subsequently spectrally differentiated by cryogenic ion trap vibrational spectroscopy. Based on the spectra of the pure complexes in a small diastereomer-specific spectral range, the composition of diastereomeric mixtures is characterized using the cosine similarity score, from which the enantiomeric ratio in the solution is determined. The method is demonstrated for acidified alanine solutions and using three different chiral selectors (2-butanol, 1-phenylethanol, 1-amino-2-propanol). Among these, 2-butanol is the best choice as a selector for protonated alanine, also because the formation ratio of the corresponding diastereomeric complexes is found to be independent of the nature of the enantiomer. Subsequently, a microfluidic chip is implemented to mix enantiomerically pure alanine solutions continuously and determine the enantiomeric ratio online with minimal sample consumption within one minute and with competitive accuracy.

Fast adiabatic transport of single laser-cooled 9Be+ ions in a cryogenic Penning trap stack

High precision mass and g-factor measurements in Penning traps have enabled groundbreaking tests of fundamental physics. The most advanced setups use multi-trap methods, which employ transport of particles between specialized trap zones. Present developments focused on the implementation of sympathetic laser cooling will enable significantly shorter duty cycles and better accuracies in many of these scenarios. To take full advantage of these increased capabilities, we implement fast adiabatic transport concepts developed in the context of trapped-ion quantum information processing in a cryogenic Penning trap system. We show adiabatic transport of a single 9Be+\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^9\ extrm{Be}^+$$\\end{document} ion initially cooled to 2 mK over a 2.2-cm distance within 15 ms and with less than 10 mK energy gain at a peak velocity of 3 m/s. These results represent an important step towards the implementation of quantum logic spectroscopy in the (anti-)proton system. Applying these developments to other multi-trap systems has the potential to considerably increase the data-sampling rate in these experiments.

Correlation of the Charge Resonance Interaction with Cluster Conformations Probed by Electronic Spectroscopy of Dimer Radical Cations of CO2 and CS2 in a Cryogenic Ion Trap.

Radical cations of dimeric clusters of carbon dioxide/disulfide, [(CX2)2]+• (X = O and S), form strong intracluster bonds through charge resonance (CR) interactions. We herein performed electronic photodissociation spectroscopy of [(CX2)2]+• while regulating the temperature under ambient and cryogenic conditions using a quadrupole ion trap. Both ions exhibited broad band absorption in the near-infrared-visible light region; it is called the "CR band", as a measure of the strength of the CR interaction. Strikingly, this band underwent a noticeable blue shift upon cryogenic cooling for [(CS2)2]+• while not for [(CO2)2]+•. On the basis of quantum chemical calculations with a coupled cluster method, the band shift was attributed to the variations in the relative population of two energetically close conformers found for [(CS2)2]+•. This study highlights a strong correlation between CR interactions and conformation of the radical dimer cations, demonstrating the exceptional significance of cryogenic cooling in the chemistry of ionic molecular clusters.

Bond dissociation energy of FeCr+ determined through threshold photodissociation in a cryogenic ion trap.

The bond dissociation energy of FeCr+ is measured using resonance enhanced photodissociation spectroscopy in a cryogenic ion trap. The onset for FeCr+ → Fe + Cr+ photodissociation occurs well above the lowest Cr+(6S, 3d5) + Fe(5D, 3d64s2) dissociation limit. In contrast, the higher energy FeCr+ → Fe+ + Cr photodissociation process exhibits an abrupt onset at the energy of the Cr(7S, 3d54s1) + Fe+(6D, 3d64s1) limit, enabling accurate dissociation energies to be extracted: D(Fe-Cr+) = 1.655 ± 0.006eV and D(Fe+-Cr) = 2.791 ± 0.006eV. The measured D(Fe-Cr+) bond energy is 10%-20% larger than predictions from accompanying CAM (Coulomb Attenuated Method)-B3LYP and NEVPT2 and coupled cluster singles, doubles, and perturbative triples electronic structure calculations, which give D(Fe-Cr+) = 1.48, 1.40, and 1.35eV, respectively. The study emphasizes that an abrupt increase in the photodissociation yield at threshold requires that the molecule possesses a dense manifold of optically accessible, coupled electronic states adjacent to the dissociation asymptote. This condition is not met for the lowest Cr+(6S, 3d5) + Fe(5D, 3d64s2) dissociation limit of FeCr+ but is satisfied for the higher energy Cr(7S, 3d54s1) + Fe+(6D, 3d64s1) dissociation limit.

Leak-out spectroscopy as alternative method to rare-gas tagging for the Renner-Teller perturbed HCCH+ and DCCD+ ions.

Infrared messenger-tagging predissociation action spectroscopy (IRPD) is a well-established technique to record vibrational spectra of reactive molecular ions. One of its major drawbacks is that the spectrum of the messenger-ion complex is taken instead of that of the bare ion. In particular for small open-shell species, such as the Renner-Teller (RT) affected HCCH+ and DCCD+, the attachment of the tag may have a significant impact on the spectral features. Here we present the application of the novel leak-out spectroscopy (LOS) as a tag-free method to record the cis-bending of the HCCH+ (∼700 cm-1) and DCCD+ cations (∼520 cm-1), using a cryogenic ion trap end user station at the FELIX laboratory. We demonstrate that the obtained LOS spectrum is equivalent to a previously recorded laser-induced reactions (LIR) spectrum of HCCH+. The bending modes are the energetically lowest-lying vibrational modes targeted with LOS so far, showing its potential as a universal broadband spectroscopic technique. Furthermore, we have investigated the effect of the rare gas attachment by recording the vibrational spectra of Ne- and Ar-tagged HCCH+. We found that the Ne-attachment led to a shift in band positions and change in relative intensities, while the Ar-attachment even led to a complete quenching of the RT splitting, showing the importance of using a tag-free method for RT affected systems. The results are interpreted with the help of high-level ab initio calculations in combination with an effective Hamiltonian approach.

Mid-infrared spectroscopy of 1-cyanonaphthalene cation for astrochemical consideration.

We present the low temperature gas-phase vibrational spectrum of ionised 1-cyanonaphthalene (1-CNN+) in the mid-infrared region. Experimentally, 1-CNN+ ions are cooled below 10 K in a cryogenic ion trapping apparatus, tagged with He atoms and probed with tuneable radiation. Quantum-chemical calculations are carried out at a density functional theory level. The spectrum is dominated by the CN-stretch at 4.516 μm, with weaker CH modes near 3.2 μm.