Resonance Ionization Spectroscopy Research Articles

Laser Spectroscopic Characterization of Supersonic Jet-Cooled 2,6-Diazaindole (26DAI).

The article presents a comprehensive laser spectroscopic characterization of a nitrogen-rich indole derivative, namely, 2,6-diazaindole (26DAI), in the gas phase. A supersonic jet-cooled molecular beam of 26DAI was characterized using two-color resonant two-photon ionization (2C-R2PI) and laser-induced fluorescence spectroscopy (LIF) to investigate the electronic excitation. The S1 ← S0 origin transition was obtained at 33915 cm-1, which was red-shifted from that of one (indole) and two (7-azaindole) nitrogen-containing indole derivatives by 1317 and 713 cm-1, respectively. The molecular orbital and energy analysis for the S1 ← S0 transition shows the significant stabilization of LUMO on subsequent N-insertion, resulting in the lowering of the S1 ← S0 (ππ*) transition energy. The single vibronic level fluorescence spectrum from the vibrationless S1 state of the molecule was recorded. The spectrum displayed an extensive Franck-Condon activity until 2500 cm-1 for the vibrational modes of the S0 state of the 26DAI molecule. The experimental ground state vibrational frequencies were compared to the calculated ones obtained at three different levels of theories. More accurate results were found at DFT B3LYP-D4 than those at the wave function-based MP2 and CCSD levels of theories. Further, the N-H stretching frequency of 26DAI in the S0 state was measured at 3524 cm-1 using fluorescence-dip infrared (FDIR) spectroscopy. The stability of 26DAI against ionization radiation was probed by measuring the two-color photoionization energy (IE2P) of 26DAI at 71866 cm-1. The IE2P value is significantly higher than those of N-poor counterparts (indole and 7-azaindole). The NBO charges and spin density (SD) values of the 26DAI molecule have shown that electronegative N(6) makes the cationic ground state less stable due to the position of the positive centers on the N atom. The results provided insights into the stability of N-rich biomolecules against photodamage. The current investigation can shed light on nature's way of stabilizing biomolecules with a possible N-insertion mechanism.

Resonance ionization spectroscopy of neodymium for determining a highly efficient two-step ionization scheme

Two-color two-step resonance ionization spectroscopy of neodymium (Nd) was performed to identify more than 120 even-parity autoionizing levels and their candidate J-values. The analysis of the observed autoionizing Rydberg series yielded a value of 44,560.11 (43)stat (2)sys cm−1 as a more accurate ionization potential of Nd. The saturation method was used to measure the transition cross-sections for some intense ionization transitions. From the measured cross-sections, the ionization efficiencies of some two-step ionization schemes were evaluated using the scheme cross-section formula to obtain several promising schemes.

Charge radii of thallium isotopes near the N=126 shell closure

The changes in the mean-squared charge radius of Tlg209 (N=128) and Tlm207 (N=126) relative to Tl205 have been measured for the first time using the in-source laser resonance-ionization spectroscopy technique with the Laser Ion Source and Trap (LIST) at ISOLDE (CERN). The application of the LIST suppresses the dominant background from isobaric francium isotopes and allows access to thallium nuclides with A⩾207. The characteristic kink in the charge radii at the N=126 neutron shell closure, as well as the odd-even effect similar to that in the adjacent bismuth, lead, and mercury isotopic chains, have been observed. The self-consistent theory of finite Fermi systems based on the energy density functional by Fayans reproduces the behavior of charge radii in these isotopic chains near N=126. The comparison with calculations in the framework of the relativistic mean field (RMF) approach is also presented. In the case of the Fayans functional it is a specific form of pairing interaction with the dependence on the density gradient that is essential to provide agreement with the experimental charge radii. In particular, the kink is reproduced without the inversion of g9/2 and i11/2 neutron single-particle states, which is a prerequisite to correctly describe the kink in the RMF models. Published by the American Physical Society 2024

The electron affinity of rubidium: a state selective measurement

Negative ions, which are formed when an electron is attached to a neutral system, are unique quantum systems. The lack of a long-range Coulomb force causes the inter-electronic interactions to become relatively more important. As a consequence, the independent particle model, which adequately describes atomic structure under normal conditions, breaks down. The alkali negative ions, with a closed valence s-shell, are among the simplest anionic systems. Hence, they can favorably be used to benchmark atomic theory. In this work, we have determined the electron affinity of 85Rb by measuring the relative partial photodetachment cross section of the negative ion, leaving the residual atom in the 5p 2P3/2 excited state. Resonance ionization spectroscopy allows for state selectivity and the ability to measure the Wigner s-wave threshold onset of the photodetachment process. The electron affinity of 85Rb was determined to be 485.887(6) meV.

In-gas-jet laser spectroscopy of No254 with JetRIS

Here we report online results with the in-gas-Jet Resonance Ionization Spectroscopy (JetRIS) apparatus. The S01↔P11 transition of No254 was successfully measured with sub-GHz resolution, marking a fivefold improvement over previous measurements. Recent developments in laser spectroscopy have allowed access to more exotic nuclei, but measurements of the heavy actinide region have been limited by line broadening mechanisms, limiting the precision with which nuclear properties can be deduced from the hyperfine spectrum. JetRIS provides a method to measure the heavy actinide region with a high level of sensitivity and higher resolution than previous experiments. The offline and online characterizations of the system are reported, and future perspectives are presented. Published by the American Physical Society 2024

Quadruple bonds in MoC: Accurate calculations and precise measurement of the dissociation energy of low-lying states of MoC.

In the present work, the electronic structure and chemical bonding of the MoC X3Σ- ground state and the six lowest excited states, A3Δ, a1Γ, b5Σ-, c1Δ, d1Σ+, and e5Π, have been investigated in detail using multireference configuration interaction methods and basis sets, including relativistic effective core potentials. In addition, scalar relativistic effects have been considered in the second order Douglas-Kroll-Hess approximation, while spin-orbit coupling has also been calculated. Five of the investigated states, X3Σ-, A3Δ, a1Γ, c1Δ, and d1Σ+, present quadruple σ2σ2π2π2 bonds. Experimentally, the predissociation threshold of MoC was measured using resonant two-photon ionization spectroscopy, allowing for a precise measurement of the dissociation energy of the ground state. Theoretically, the complete basis set limit of the calculated dissociation energy with respect to the atomic ground state products, including corrections for scalar relativistic effects, De(D0), is computed as 5.13(5.06) eV, in excellent agreement with our measured value of D0(MoC) of 5.136(5) eV. Furthermore, the calculated dissociation energies of the states having quadruple bonds with respect to their adiabatic atomic products range from 6.22 to 7.23eV. The excited electronic states A3Δ2 and c1Δ2 are calculated to lie at 3899 and 8057 cm-1, also in excellent agreement with the experimental values of DaBell et al., 4002.5 and 7834 cm-1, respectively.

Positive cooperativity in binding: Spectroscopic characterization and dissociation energy of the anisole…(CH4)2 complex

We have previously reported on the spectroscopy and binding energy of the anisole…methane complex, which exhibits a dual mode of binding that involves both CH/O and CH/π interactions. In this work, we seek to examine cooperativity in binding through a study of the isolated anisole-(methane)2 complex, using a combination of experiments that include mass-selected two-color resonant two-photon ionization spectroscopy (2CR2PI), two-color appearance potential (2CAP) measurements, and velocity mapped ion imaging (VMI) augmented with a complementary theoretical characterization. Using 2CAP and VMI, we derive the dissociation energies of the complex in ground (S0), excited (S1), and cation radical (D0) states. The experimental values from the two methods are in excellent agreement and are compared with selected theoretical values calculated using DFT and ab initio methods. The data show that the dissociation energy increases by some 10 % for the second methane relative to the first, with this trend being consistent across all three electronic states, indicating a cooperative binding effect where the initial solvation turns on binding of a second methane onto the opposite face. This lies in contrast to the aniline-(methane)2 complex, where recent studies have shown a negativity cooperativity, and these trends are examined.

Resonant laser ionization of neptunium: investigation on excitation schemes and the first ionization potential

The atomic structure of neptunium (Np) was investigated by two-step resonance ionization spectroscopy. The study involved exploring ground-state transitions as well as following transitions to high-lying states just below the ionization potential (IP) or auto-ionizing states above the IP. That resulted in the identification of two-step ionization schemes, suitable for trace analysis and nuclear structure investigations. The lifetimes of two excited states located at 25,342.48 cm-1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\, \ ext {cm}^{-1} $$\\end{document} and 25,277.64 cm-1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\, \ ext {cm}^{-1} $$\\end{document} were determined as 230(12) ns and 173(9) ns, respectively. Because of the absence of Rydberg series in wide-ranging spectra recorded, the first IP was determined through the field ionization of high-lying, weakly-bound states using a well-controlled static electric field. By applying the saddle-point model, an IP value of 50,535.54(15) cm-1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{-1}$$\\end{document} [6.265608(19) eV] was derived. This value agrees with the current literature value of 50,535(2) cm-1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{-1}$$\\end{document}, while providing a more than ten times higher precision.Graphic abstract

Magnetic moments of thallium isotopes in the vicinity of magic N = 126

The magnetic dipole moments (μ) of 209Tlg (N=128) and 207Tlm (N=126) have been measured for the first time using the in-source laser resonance-ionization spectroscopy technique with the Laser Ion Source and Trap (LIST) at ISOLDE (CERN). The application of the LIST suppresses the usually overwhelming background of the isobaric francium isotopes and allows access to heavy thallium isotopes with A⩾207. The self-consistent theory of finite Fermi systems based on the energy density functional by Fayans et al. well describes the N dependence of μ for 1/2+ thallium ground states, as well as μ for the 11/2− isomeric states in europium, gold and thallium isotopes. The inclusion of particle-vibration coupling leads to a better agreement between the theory and experiment for μ(Tlg, Iπ=1/2+). It is shown that beyond mean-field contributions to μ cannot be neglected at least for thallium isotopes with Iπ=1/2+.

Spectroscopic characterization of the complexes of 2-(2'-pyridyl)-benzimidazole and (H2O)1,2, (CH3OH)1,2, and (NH3)1,2 isolated in the gas phase.

The hydrogen-bonded docking preferences of small solvent molecules on 2-(2'-pyridyl)-benzimidazole (PBI) were studied experimentally aided by computational findings. The PBI-S1,2 complexes (S = H2O, CH3OH, and NH3) were produced in a supersonically jet-cooled molecular beam and probed using resonant two-photon ionization and laser-induced fluorescence spectroscopy, with multiple isomers confirmed by UV-UV hole-burning spectroscopy. Two distinct isomers of PBI-H2O and PBI-(H2O)2 complexes were identified, while PBI-CH3OH and PBI-NH3 each formed a single 1 : 1 and 1 : 2 complex. Computational results with experimental findings revealed PBI-S-a as the most stable structure, with a solvent molecule forming a hydrogen-bonded bridge between imidazolyl-NH (NIH) and pyridyl-N (NP) at site-a. The site-a isomers exhibit higher S1 state stability compared to the S0 state, resulting in red-shifted S0 → S1 band origin for PBI-S-a and a further red-shift for the PBI-(S)2-aa isomers. In contrast, the PBI-S-b isomer, with a hydrogen bond between imidazolyl-N (NI) and pyridyl-CH (CPH) at site-b opposite to site-a, showed a blue-shifted band origin transition. A unique PBI-(H2O)2-ab isomer was detected with solvent molecules bound at both sites a and b, displaying a smaller red-shift in the band origin transition than the aa-isomer. The energy barrier for solvent-to-chromophore proton transfer varies with isomeric configuration. PBI-H2O-b isomers show significantly higher barriers (>800 cm-1), while PBI-(H2O)-aa has a slightly increased barrier (>436 cm-1) compared to the PBI-H2O-a (420 ± 10 cm-1) isomer. This study explores the potential landscape of PBI, enhancing our understanding of stabilization effects, spectral shifts, and their impact on chromophore excited-state dynamics in various environments.

The Double-Nozzle Technique Equipped with RF-Only Funnel and RF-Buncher for the Ion Beam Extraction into Vacuum

This study is a further development of our “Proposal of a new double-nozzle technique for in-gas-jet laser resonance ionization spectroscopy” paper published in the journal Atoms earlier this year. Here, we propose equipping the double-nozzle technique with the RF-only funnel and RF-buncher placed in a gas-jet chamber at a 70 mm distance downstream of the double-nozzle exit. It allows for highly effective extraction into vacuum heavy ion beams, produced in two-steps laser resonance ionization in the argon supersonic jet. We explored the operation of this new full version of the double-nozzle technique through detailed gas dynamic and Monte Carlo trajectory simulations, with the results presented and discussed. In particular, our calculations showed that more than 80% of all nobelium-254 neutral atoms, extracted by argon flow from the gas-stopping cell, can then be extracted into vacuum in a form of pulsed ion beam having low transverse and longitudinal emittance.

Modern methods for identification of atoms, molecules, and aerosols in various objects

The study is aimed at developing highly sensitive methods of laser analytical spectroscopy. The physical mechanisms of forming useful signals (selective ionization signal and cavity ring-down signal) were identified that provided registration of parameters of atomic and aerosol systems in the intensive pulsed laser field. High-sensitive laser methods of laser resonance ionization spectroscopy in vacuum, laser-enhanced ionization spectrometry in flame, and cavity ringdown laser absorption spectroscopy (CRLAS) are used for the determination of ultra-small concentrations of atoms in different phase states of the substance. Samples of aqueous standard solutions and solid metals of s (Li, K, Na, Ca, Cs), p (Al, In), d (Cr, Mn, Fe, Co, Ni, Cu, Ag, Au, Pt, Zn, Hg), f (Yb) elements, aluminum alloys, especially pure solvents, crystals (NH4F, NaF), semi-conductor materials (GaAs, Si) and various aerosols of salts (NaCl, CsCl, NaI, NaF, KCl AgNO3), chemicals, organic dyes, alloys, soils and rocks were studied. The new mechanisms of getting free particles are revealed and new methods increasing the efficiency of atomization, selective ionization and excitation of atoms in systems «flame», «rod – flame», in atomizer «graphite – furnace» are proposed. The particle size distribution of aerosols formed under the impact of high-power laser radiation on the surface of a solid sample has been studied. The dependence of the absolute concentration of aerosol particles on their size has been determined. Aerosol extinction coefficients and extinction efficiency have been measured using intracavity laser spectroscopy. For the first time new parameters of aerosols are revealed by physical and chemical properties of aerosol plumes from solid surfaces and aerosols of salt of metals and organic aerosols. Methods of additives and calibration curve were used to examine the effects of the matrix on the analytical signal of the studied atoms.

RAPTOR: A new collinear laser ionization spectroscopy and laser-radiofrequency double-resonance experiment at the IGISOL facility

RAPTOR, Resonance ionization spectroscopy And Purification Traps for Optimized spectRoscopy, is a new collinear resonance ionization spectroscopy device constructed at the Ion Guide Isotope Separator On-Line (IGISOL) facility at the University of Jyväskylä, Finland. By operating at beam energies of under 10keV, the footprint of the experiment is reduced compared to more traditional collinear laser spectroscopy beamlines. In addition, RAPTOR is coupled to the JYFLTRAP Penning trap mass spectrometer, opening a window to laser-assisted nuclear-state selective purification, serving not only the mass measurement program, but also supporting post-trap decay spectroscopy experiments. Finally, the low-energy ion beams used for RAPTOR will enable high-precision laser-radiofrequency double-resonance experiments, resulting in spectroscopy with linewidths below 1 MHz. In this contribution, the technical layout of RAPTOR and a selection of ion-beam optical simulations for the device are presented, along with a discussion of the current status of the commissioning experiments.

Opportunities and limitations of in-gas-cell laser spectroscopy of the heaviest elements with RADRIS

The radiation detection resonance ionization spectroscopy (RADRIS) technique enables laser spectroscopic investigations of the heaviest elements which are produced in atom-at-a-time quantities from fusion-evaporation reactions. To achieve a high efficiency, laser spectroscopy is performed in a buffer-gas environment used to thermalize and stop the high-energy evaporation residues behind the velocity filter SHIP. The required cyclic measurement procedure in combination with the applied filament collection for neutralization as well as confinement of the stopped ions and subsequent pulse-heat desorption constrains the applicability of the technique. Here, some of these limitations and also opportunities that arise from this unique measurement setup will be evaluated.

Proposal of a New Double-Nozzle Technique for In-Gas-Jet Laser Resonance Ionization Spectroscopy

This paper proposes a new double-nozzle technique for in-gas-jet laser resonance ionization spectroscopy. We explored the functionality of this new technique through detailed gas dynamic and Monte Carlo atom-trajectory simulations, in which results are presented and discussed. The results of similar computer simulations for JetRIS setup (as a typical representative of the conventional in-gas-jet technique nowadays) are also presented and discussed. The direct comparison of calculation results for the proposed new technique with the conventional one shows that the double-nozzle technique has many advantages compared with the one used in the JetRIS setup at GSI for future high-resolution laser spectroscopic study of heaviest elements. To fully implement the proposed new technique in all existing (or under construction) setups for in-gas-jet laser resonance ionization spectroscopy, it will be enough to replace the used supersonic nozzle with the miniature double-nozzle device described in the paper.

Investigating radioactive negative ion production via double electron capture

The relative cross sections for radioactive negative ion production via double electron capture have been measured for collisions between a 40 keV projectile beam of uranium-238 and potassium vapor. This was performed at the collinear resonance ionization spectroscopy (CRIS) experiment at CERN-ISOLDE and is a step towards measuring the electron affinities (EAs) of elements that cannot be efficiently produced in negative ion sources at radioactive ion beam (RIB) facilities. This includes short-lived radioactive isotopes that have low production quantities and heavy and superheavy elements that systematically have smaller EAs than work functions of available ion source materials. Negative ions are particularly sensitive to electron–electron correlation effects, which make such studies ideal for benchmarking atomic structure models that go beyond the independent particle model. While the EAs of most light elements have been measured, experimental investigations on heavier elements, namely the actinides, remain scarce due to their radioactive nature and production difficulty. By developing negative ion production by charge exchange, we aim to make these studies feasible at RIB facilities.

Voltage scanning and technical upgrades at the Collinear Resonance Ionization Spectroscopy experiment

To optimize the performance of the Collinear Resonance Ionization Spectroscopy (CRIS) experiment at CERN-ISOLDE, technical upgrades are continuously introduced, aiming to enhance its sensitivity, precision, stability, and efficiency. Recently, a voltage-scanning setup was developed and commissioned at CRIS, which improved the scanning speed by a factor of three as compared to the current laser-frequency scanning approach. This leads to faster measurements of the hyperfine structure for systems with high yields (more than a few thousand ions per second). Additionally, several beamline sections have been redesigned and manufactured, including a new field-ionization unit, an electrostatic bend with a larger deflection angle, and improved ion optics. The beamline upgrades are expected to yield an improvement of at least a factor of 5 in the signal-to-noise ratio by avoiding the use of high-power lasers (which yield non-resonantly produced ions) and providing time-of-flight separation between the resonant ions and the collisional background.

Progress in the development of a collinear resonance ionisation laser spectroscopy setup

A collinear resonance ionisation spectroscopy setup has been developed with the aim to study the nuclear properties of more exotic isotopes. It is developed on the basis of a recently-commissioned collinear laser spectroscopy, and could in principle measure the hyperfine structure spectra of studied isotopes using both laser-induced fluorescence and laser resonance ionisation approaches. In this paper, the latest technique development, the progress on the test of the vacuum system and the ion beam transportation, and the near-term offline experimental plans are presented.

Bond dissociation energies of diatomic transition metal nitrides.

Resonant two-photon ionization (R2PI) spectroscopy has been used to measure the bond dissociation energies (BDEs) of the diatomic transition metal nitrides ScN, TiN, YN, MoN, RuN, RhN, HfN, OsN, and IrN. Of these, the BDEs of only TiN and HfN had been previously measured. Due to the many ways electrons can be distributed among the d orbitals, these molecules possess an extremely high density of electronic states near the ground separated atom limit. Spin-orbit and nonadiabatic interactions couple these states quite effectively, so that the molecules readily find a path to dissociation when excited above the ground separated atom limit. The result is a sharp drop in ion signal in the R2PI spectrum when the molecule is excited above this limit, allowing the BDE to be readily measured. Using this method, the values D0(ScN) = 3.905(29) eV, D0(TiN) = 5.000(19) eV, D0(YN) = 4.125(24) eV, D0(MoN) = 5.220(4) eV, D0(RuN) = 4.905(3) eV, D0(RhN) = 3.659(32) eV, D0(HfN) = 5.374(4) eV, D0(OsN) = 5.732(3) eV, and D0(IrN) = 5.115(4) eV are obtained. To support the experimental findings, ab initio coupled-cluster calculations extrapolated to the complete basis set limit (CBS) were performed. With a semiempirical correction for spin-orbit effects, these coupled-cluster single double triple-CBS calculations give a mean absolute deviation from the experimental BDE values of 0.20eV. A discussion of the periodic trends, summaries of previous work, and comparisons to isoelectronic species is also provided.

A combined spectroscopic and computational investigation on the solvent-to-chromophore excited-state proton transfer in the 2,2'-pyridylbenzimidazole-methanol complex.

This article demonstrates experimental proof of excited state 'solvent-to-chromophore' proton transfer (ESPT) in the isolated gas phase PBI (2,2'-pyridylbenzimidazole)-CH3OH complex, aided by computational calculations. The binary complexes of PBI with CH3OH/CH3OD were produced in a supersonic jet-cooled molecular beam and the energy barrier of the photo-excited process was determined using resonant two-colour two-photon ionization spectroscopy (R2PI). The ESPT process in the PBI-CH3OH complex was confirmed by the disappearance of the Franck-Condon active vibrational transitions above 000 + 390 cm-1. In the PBI-CH3OD complex, the reappearance of the Franck-Condon transitions till 000 + 800 cm-1 confirmed the elevation of the ESPT barrier upon isotopic substitution due to the lowering of the zero-point vibrational energy. The ESPT energy barrier in PBI-CH3OH was bracketed as 410 ± 20 cm-1 (4.91 ± 0.23 kJ mol-1) by comparing the spectra of PBI-CH3OH and PBI-CH3OD. The solvent-to-chromophore proton transfer was confirmed based on the significantly decreased quantum tunnelling of the solvent proton in the PBI-CH3OD complex. The computational investigation resulted in an energy barrier of 6.0 kJ mol-1 for the ESPT reaction in the PBI-CH3OH complex, showing excellent agreement with the experimental value. Overall, the excited state reaction progressed through an intersection of ππ* and nπ* states before being deactivated to the ground state via internal conversion. The present investigation reveals a novel reaction pathway for the deactivation mechanism of the photo-excited N-containing biomolecules in the presence of protic-solvents.