Excited Atomic States Research Articles

Electron scattering on molecular nitrogen: common gas, uncommon cross sections

We discuss peculiar features of electron scattering on the N2 molecule and the N2+ ion, that are important for modeling plasmas, Earth’s and other planets’ atmospheres. These features are, among others: the resonant enhancement of the vibrational excitation in the region of the shape resonance around 2.4 eV, the resonant character of some of electronic excitation channels (and high values of these cross sections, both for triplet and singlet states), high cross section for the dissociation into neutrals, high cross sections for elastic scattering (and electronic transitions) on metastable states. For the N2+ ion we discuss both dissociation and the dissociative ionization, leading to the formation of atoms in excited states, and dissociative recombination which depends strongly on the initial vibrational state of the ion. We conclude that the theory became an indispensable completion of experiments, predicting many of partial cross sections and their physical features. We hope that the data presented will serve to improve models of nitrogen plasmas and atmospheres.Graphical abstract

On the importance of excited state species in low pressure capacitively coupled plasma argon discharges

In the past three decades, first principles-based fully kinetic particle-in-cell Monte Carlo collision (PIC/MCC) simulations have been proven to be an important tool for the understanding of the physics of low pressure capacitive discharges. However, there is a long-standing issue that the plasma density determined by PIC/MCC simulations shows quantitative deviations from experimental measurements, even in argon discharges, indicating that certain physics may be missing in previous modeling of the low pressure radio frequency (rf) driven capacitive discharges. In this work, we report that the energetic electron-induced secondary electron emission (SEE) and excited state atoms play an important role in low pressure rf capacitive argon plasma discharges. The ion-induced secondary electrons are accelerated by the high sheath field to strike the opposite electrode and produce a considerable number of secondary electrons that lead to additional ionizing impacts and further increase of the plasma density. Importantly, the presence of excited state species even further enhances the plasma density via excited state neutral and resonant state photon-induced SEE on the electrode surface. The PIC/MCC simulation results show good agreement with the recent experimental measurements in the low pressure range (1–10 Pa) that is commonly used for etching in the semiconductor industry. At the highest pressure (20 Pa) and driving voltage amplitudes 250 and 350 V explored here, the plasma densities from PIC/MCC simulations considering excited state neutrals and resonant photon-induced SEE are quantitatively higher than observed in the experiments, requiring further investigation on high pressure discharges.

Faraday rotation and ellipticity spectroscopy between excited states of Rb vapor: Theory and experiment

The Faraday rotation and ellipticity spectra of rubidium $5{P}_{3/2}\ensuremath{\rightarrow}4{D}_{5/2}$ transition in a magnetic field have been calculated and experimentally measured. By using the rotating quarter-wave plate method, the Stokes parameters of the $5{P}_{3/2}\ensuremath{\rightarrow}4{D}_{5/2}$ near-resonant probe light are measured to obtain the Faraday rotation and the ellipticity. The variation of the rotation and the ellipticity spectra is analyzed in different magnetic fields, temperatures, and pump powers. The polarization rotation over 50 deg in 1529 nm with negligible elliptical distortion is obtained. Our study of the Faraday effect between excited states of atoms broadens the available wavelength of the Faraday effect in applications.

High-Sensitivity Rydberg-Atom-Based Phase-Modulation Receiver for Frequency-Division-Multiplexing Communication

Due to the exaggerated properties of highly excited atomic states, a Rydberg-atom-based microwave receiver holds the promise to achieve superior performances in microwave metrology and communication when compared to conventional antennas. However, developing long-distance communication applications based on Rydberg atomic receiver remains challenging, because it requires the simultaneous achievement of low bit error rate (BER), high symbol rate, and weak carrier amplitude. The key to tackle this problem is to encode the information with a proper scheme that maintains high sensitivity and robustness of the Rydberg atomic receiver. Here, we use Rydberg atom-based heterodyne detection for the reception of phase-modulated microwave field, and demonstrate more than one order of magnitude improvement in reception sensitivity compared to the previously investigated amplitude-modulation scheme. Therefore, we achieve low BER communication with high symbol rate of 12 k bit/s and weak carrier amplitude of $13\phantom{\rule{0.2em}{0ex}}\text{\ensuremath{\mu}}\mathrm{V}\phantom{\rule{0.2em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$ simultaneously. Furthermore, we also demonstrate that our scheme is compatible with frequency-division-multiplexing communication.

Measuring autoionization decay lifetimes of optically forbidden inner valence excited states in neon atoms with attosecond noncollinear four-wave-mixing spectroscopy

Attosecond noncollinear four wave mixing spectroscopy with one attosecond extreme ultraviolet (XUV) pulse and two few-cycle near-infrared (NIR) pulses was used to measure the autoionization decay lifetimes of inner valence electronic excitations in neon atoms. After a 43-48 eV XUV photon excites a 2s electron into the 2s2p6[np] Rydberg series, broadband NIR pulses couple the 2s2p6[3p] XUV-bright state to neighboring 2s2p6[3s] and 2s2p6[3d] XUV-dark states. Controllable delays of one or both NIR pulses with respect to the attosecond XUV pulse reveal the temporal evolution of either the dark or bright states, respectively. Experimental lifetimes for the 3s, 3p, and 3d states are measured to be 7 +/- 2 fs, 48 +/- 8 fs, and 427 +/- 40 fs, respectively, with 95% confidence. Accompanying calculations with two independent ab initio theoretical methods, NewStock and ASTRA, verify the findings. The results support the expected trend that the autoionization lifetime should be longer for states that have a smaller penetration in the radial region of the 2s core hole, which in this case is for the higher angular momentum Rydberg orbitals. The underlying theory thus links the lifetime results to electron correlation and provides an assessment of the direct and exchange terms in the autoionization process.

Kinetics of Metastable Argon Optical Excitation and Gain in Ar/He Microplasmas.

The optically pumped rare-gas metastable laser is capable of high-intensity lasing on a broad range of near-infrared transitions for excited-state rare gas atoms (Ar*, Kr*, Ne*, Xe*) diluted in flowing He. The lasing action is generated by photoexcitation of the metastable atom to an upper state, followed by collisional energy transfer with He to a neighboring state and lasing back to the metastable state. The metastables are generated in a high-efficiency electric discharge at pressures of ∼0.4 to 1 atm. The diode-pumped rare-gas laser (DPRGL) is a chemically inert analogue to diode-pumped alkali laser (DPAL) systems, with similar optical and power scaling characteristics for high-energy laser applications. We used a continuous-wave linear microplasma array in Ar/He mixtures to produce Ar(1s5) (Paschen notation) metastables at number densities exceeding 1013 cm-3. The gain medium was optically pumped by both a narrow-line 1 W titanium-sapphire laser and a 30 W diode laser. Tunable diode laser absorption and gain spectroscopy determined Ar(1s5) number densities and small-signal gains up to ∼2.5 cm-1. Continuous-wave lasing was observed using the diode pump laser. The results were analyzed with a steady-state kinetics model relating the gain and the Ar(1s5) number density.

Editorial: Strong field physics and attosecond science

emission from Rydberg atoms. Substantial neutral atoms can be excited after tunneling in a strong laser 14 field, in the process known as frustrated tunneling ionization. The generation of coherent emission from 15 the excited-state atoms produced by the frustrated tunneling ionization is demonstrated to be dependent on 16 the chirp of the laser pulse. This chirp dependence also provides a new way to investigate the dynamics 17 of Rydberg states. Kong et al. (Kong et al., 2022) explored the influence of mechanical strains on the 18 high-order harmonic generation in the monolayer hexagonal boron nitride crystal by using time-dependent 19 density functional theory. They found the band structure is sensitive to the structural deformation modulated 20 by strains. This result may be useful in probing lattice deformations in crystals and heuristic to enhance the 21 optoelectronic efficiency of solid-state nano-devices. In conclusion, the Research Topic is created to present the latest advances and trends concerning the 62 strong field physics and attosecond science. Our special thanks to the Frontiers in Physics team for the 63 technical assistance with publishing. Much more efforts are still ongoing in this fascinating area. We expect 64 that this field will attract more and more attentions and benefit potential applications.

Estimation of prolonged lifetimes of excited states of neutral oxygen atom (OI) by time-resolved laser-induced breakdown spectroscopy (TR-LIBS)

Lifetimes of the upper states of excited oxygen atoms corresponding to transitions to the common lower state in the case of the emission lines around 777 nm and 844 nm have been estimated by measuring the line intensities as a function of the delay time between the Q-switching of the laser and the opening of the window of the ICCD. In the case of the emission line around 777 nm, resulting from the transitions from the three very closely spaced upper energy levels, 2s2 2p3 (4S0) 3p5P3 (777.194 nm), 2s2 2p3 (4S0) 3p5P2 (777.417 nm) and 2s2 2p3 (4S0) 3p5P1 (777.539 nm) to the common lower energy level 2s2 2p3 (4S0) 3s5S2, the lifetime was measured to be 253 ns. Similarly, in the case of the emission-line around 844 nm, resulting from the transitions from the three very closely spaced upper energy levels 2s2 2p3 (4S0) 3p3P0 (844.625 nm), 2s2 2p3 (4S0) 3p3P2 (844.636 nm) and 2s2 2p3 (4S0) 3p3P1 (844.676 nm) to the common lower energy level 2p3 (4S0) 3s3S1, the lifetime was measured to be 278 ns by this technique. The measured lifetimes in our experiment, for both 777 nm and 844 nm atomic transition lines of oxygen (O), are almost nine times higher than the theoretical value. Self-absorption and radiation trapping are possible mechanisms responsible for the mismatch between measured and intrinsic lifetimes. Last but not least, utilizing the TR-LIBS technique is yet another incredible application to estimate the prolonged lifetime of closely spaced excited states of an atom in the presence of self-absorption and radiation trapping. The average plasma cooling temperature (excitation temperature) lifetime was found to be 1183 ns, which is compatible with the previously reported values. J. Bangladesh Acad. Sci. 46(2); 175-183: December 2022

A Photochemical Macrocyclization Route to Asymmetric Strained [3.2] Paracyclophanes.

The intricate frameworks of paracyclophanes are an important target for synthesis since they are found in various chiral auxiliaries, solar cells, high-performance plastics, pharmaceuticals, and molecular machines. Whereas numerous methods exist for the preparation of symmetric paracyclophanes, protocols for the efficient synthesis of strained asymmetric scaffolds are limited. Here we report a remarkably simple photochemical route to strained [3.2]paracyclophanes starting from readily available educts. By way of NMR and X-ray analyses, we discovered that UV-irradiation of an aromatic carboxylic ester tethered to a toluene moiety leads to the intramolecular formation of a new C-C bond, with loss of an alcohol. A systematic evaluation of the reaction conditions and substituents, as well as radical starter and triplet quenching experiments, point to a reaction mechanism involving an excited triplet state and hydrogen atom transfer. The new method proved to be robust and versatile enabling the synthesis of a range of cyclophanes with different substitutions, including an unusual diastereoisomer with two planar chiral centers, and thus proved to be a valuable addition to the synthetic toolbox.

Probing La and Ce Excited-State Reactivity with Resonant Two-Photon Ionization Spectroscopy.

Dehydrogenation and C-C bond cleavage of 1-butyne by the excited states of La and Ce atoms are investigated in laser-ablation metal molecular beams. The excited states of the metal atoms are prepared by resonant excitation, detected by resonant two-photon ionization spectroscopy, and the reaction products are monitored by photoionization time-of-flight mass spectrometry. The reactivities of La* [5d2(3F)6p (4G5/2°)] and Ce* [4f5d(3F°)6s6p(3P°) (5H5)] excited states are observed to be higher than those of the initial states of the corresponding metal atoms. The higher reactivities of the excited states are attributed to their higher energies and favorable electron configurations to form two covalent bonds of the metal-insertion intermediates. Although both excited La and Ce atoms show increased reactivities, the enhancement for Ce is much more pronounced than that of La, which cannot be explained by electron configurations alone. The larger reactivity enhancement from the initial states to the excited state of the Ce atom than that of La is due to the longer lifetime of the Ce excited state.

Puzzling time properties of proportional electroluminescence in two-phase argon detectors for dark matter searches

Proportional electroluminescence (EL) in noble gases is a physical process routinely used in two-phase (liquid–gas) detectors for low-energy astroparticle-physics experiments. In this work, the time properties of visible-light EL in two-phase argon detectors have been systematically studied for the first time. In particular, two unusual slow components in the EL signal, with their contributions and time constants increasing with electric field, were observed. This puzzling property is not expected in any of the known mechanisms of photon and electron emission in two-phase media. Time constants of these components is about 4–5 upmu s and 50 upmu s. In addition, a specific threshold behavior of the slow components was revealed: they emerged at a threshold in reduced electric field of 4.8 ± 0.2 Td regardless of the gas phase density, which is about 1 Td above the onset of standard (excimer) EL. There is a conspicuous similarity between this threshold and reduced field threshold of EL in NIR occurring via higher atomic excited states Ar^{*}(3p^{5}4p). An unexpected temperature dependence of slow components was also observed: their contribution decreased with temperature, practically disappearing at room temperature. We show that the puzzling properties of slow components can be explained in the framework of hypothesis that these are produced in the charge signal itself due to trapping of drifting electrons on metastable negative argon ions.

Optically end-pumped scheme in rubidium vapor: Theory and experiment

The optimal detuning of the pump light at the rubidium D2 line is calculated and experimentally validated. A three-level optically end-pumped model in a hot rubidium vapor cell is demonstrated, which takes into account the hyperfine structure of the ground state, various collisional processes, and the nonlinear absorption of the pump light along the cell length. By developing a constrained optimization model, we calculate the optimal detuning of the pump light that maximizes the average excited state atom concentration in the cell. Experimentally, a 1529 nm probe light at higher levels, which is attenuated to the weak-probe limit, is introduced to accurately characterize the excited state atom concentration. Coupling with the experimental results, the variation of the pump light optimal detuning with the temperature and the pump light intensity at the unsaturated pumping is analyzed. At the optimal detuning point, the theoretical decay function of the pump light percentage along the vapor cell length almost coincides regardless of the temperature and the pump light intensity changes. Moreover, the theoretical fitted pump light decay function at optimal detuning is predicted. The fitted pump light percentage exiting the vapor cell is 4.75%. A fast implementation method to achieve the maximal average excited state atom concentration in the experiment is demonstrated.

Particle-in-Cell Simulations With Fluid Metastable Atoms in Capacitive Argon Discharges: Electron Elastic Scattering and Plasma Density Profile Transition

Particle-in-cell/Monte Carlo collision (PIC/MCC) simulations are an important tool for understanding low-temperature plasma dynamics, and benchmark work is needed to build a solid base for the correctness of PIC/MCC codes. In our recent publication (Wen <italic xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">et al.</i> , 2021), benchmarking of the object-oriented PIC/MCC oopd1 code was performed against the well-established <monospace xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">xpdp1</monospace> code for a simplified argon reaction set. Furthermore, oopd1 was upgraded to incorporate the excited state atoms as space- and time-varying fluids. Here, we show more details and perform further analysis of the benchmark work. The plasma density profile transition is further explored; the “passively” flat plasma density profile in the absence of metastables is found to be parabolic at low pressure and flat at 1.6 and 5 Torr. In the presence of metastable atoms, the “parabolic” profile at 5 Torr becomes “flat” at 15 Torr due to the reduced excited state atom density in the discharge center, which decreases the step-wise ionization rates. In addition, the effects of electron elastic scattering, i.e., Coulomb-screening-based non-isotropic scattering, total elastic (and momentum transfer) cross-section-dependent non-isotropic scattering, and momentum transfer isotropic scattering on capacitive discharges, are examined, showing that at a low pressure of 50 mTorr Coulomb-screening-based scattering underestimates the plasma density and electron power absorption by around 15%. However, isotropic scattering and cross-section-dependent non-isotropic scattering give almost the same plasma density and electron power absorption. At a higher pressure of 1.6 Torr, the plasma properties are independent of electron scattering in the presence of metastable atoms. In the absence of metastable atoms, different electron scattering treatments bring a few percent difference for plasma density and electron power absorption.

Atomic excited states and the related energy levels.

This article is about generalization and extension of the Bohr atomic model as well as the Rydberg formula to make them applicable to all atomic/ionic excited states and their energy levels. Bohr and Rydberg's original works were deemed only for hydrogen and the hydrogen-like ions but in time many mistakenly have come to the conclusion that those original forms of the theory are applicable to all species. This article clarifies the subject and helps with the misunderstandings. The article reviews first the original theory of atoms, the related excited states, and the related energy levels. It then shows the shortcoming of the original formulations and makes changes to generalize the theory and extend their applications to all atoms and their related ions. The theory of atomic excited states is re-formulated using a newly defined parameter called "characteristic exponent k" and the corresponding ionization energy. Numerical calculations and detailed works for several elements are presented to establish a better understanding of excited states. The article seeks also for a connection between the atomic energy levels and the internal structures and inner electrons of atoms. Furthermore, a small data bank is generated using the calculated "characteristic exponents k" for elements to be utilized for future simulations, studies, and research activities.

Influence of the size of iron nanoclusters on their magnetization

The size of iron nanocrystals significantly affects the value of their magnetization. However, an adequate model of the structure of nanocrystalline formations comprising different numbers of iron atoms still does not exist. In this work, spatial models of nanocrystalline iron clusters differing in configuration and the number of their constituent atoms are constructed. Tetrahedrally close-packed cluster assemblies of iron atoms are taken as the basis for the proposed structures of nanocrystals. The spectra of the density of electronic states for the proposed clusters are constructed using the theory of the electron density functional. The calculation was carried out by the method of scattered waves in accordance with the band theory of crystals. The appearance of magnetization in tetrahedral close-packed cluster formations is associated with excited electronic states of atoms located on the surface of the nanocluster. Excited atoms have an increased electron density, that is, electrons are able to transition to states with higher energy, approaching the Fermi energy. In this case, the Stoner criterion necessary for the occurrence of magnetization is fulfilled. The configurations of electrons with spin up and down differ, which is why uncompensated magnetic moments appear. It is shown that the proposed models of iron nanoclusters are in satisfactory agreement with the known experimental data.

Non-Markovian dynamics of a single excitation within many-body dissipative systems

We explore the dynamics of $N$ coupled atoms to a generic bosonic reservoir under specific system symmetries. In the regime of multiple atoms coupled to a single reservoir with identical couplings, we identify remarkable effects, notably that the initial configuration of the atomic excited state amplitudes strongly impacts the dynamics of the system and can even fully sever the system from its environment. Additionally, we find that steady state amplitudes of the excited states become independent of the choice of the reservoir. The framework introduced is applied to a structured photonic reservoir associated with a photonic crystal, where we show it reproduces previous theoretical and experimental results and it predicts superradiant behaviour within the single-excitation regime.

Photoionization cross sections of ultracold 88Sr in 1P1 and 3S1 states at 390 nm and the resulting blue-detuned magic wavelength optical lattice clock constraints.

We present the measurements of the photoionization cross sections of the excited 1P1 and 3S1 states of ultracold 88Sr atoms at 389.889 nm wavelength, which is the magic wavelength of the 1S0-3P0 clock transition. The photoionization cross section of the 1P1 state is determined from the measured ionization rates of 88Sr in the magneto-optical trap in the 1P1 state to be 2.20(50)×10-20 m2, while the photoionization cross section of 88Sr in the 3S1 state is inferred from the photoionization-induced reduction in the number of atoms transferred through the 3S1 state in an operating optical lattice clock to be 1.38(66) ×10-18 m2. Furthermore, the resulting limitations of employing a blue-detuned magic wavelength optical lattice in strontium optical lattice clocks are evaluated. We estimated photoionization induced loss rates of atoms at 389.889 nm wavelength under typical experimental conditions and made several suggestions on how to mitigate these losses. In particular, the large photoionization induced losses for the 3S1 state would make the use of the 3S1 state in the optical cycle in a blue-detuned optical lattice unfeasible and would instead require the less commonly used 3D1,2 states during the detection part of the optical clock cycle.

Terahertz electrometry via infrared spectroscopy of atomic vapor

In recent years, the characterization of radiation falling within the so-called “terahertz (THz) gap” has become an ever more prominent issue due to the increasing use of THz systems in applications such as nondestructive testing, security screening, telecommunications, and medical diagnostics. THz detection technologies have advanced rapidly, yet traceable calibration of THz radiation remains challenging. In this paper, we demonstrate a system of electrometry in which a THz signal can be characterized using laser spectroscopy of highly excited (Rydberg) atomic states. We report on proof-of-principle measurements that reveal a minimum detectable THz electric field amplitude of 1.07 ± 0.06 V / m at 1.06 THz (3 ms detection), corresponding to a THz power at the atomic cell of approximately 3.4 nW. Due to the relative simplicity and cryogen-free nature of this system, it has the potential to provide a route to a SI traceable “atomic candle” for THz calibration across the THz frequency range, and provide an alternative to calorimetric methods.

Generation and Characterization of the Charge-Transferred Diradical Complex CaCO2 with an Open-Shell Singlet Ground State

The CaCO2 complex is generated via the reaction of excited-state calcium atom with carbon dioxide in a solid neon matrix. Infrared absorption spectroscopy and quantum chemical calculations reveal that the complex has a planar four-membered ring structure with a strongly bent CO2 ligand side-on coordinated to the calcium center in an η2-O, O manner. The complex has an open-shell singlet ground state, which can be described as the bonding interactions between a Ca+ (4s1) cation in the doublet ground state and a doublet ground state CO2- anion. The analysis of the bonding situation suggests that the Ca-O2C bonds have a large (75%) electrostatic character. The covalent (orbital) interactions come from the coupling of the unpaired electrons of Ca+ and CO2- giving rise to electron-sharing bonding and a stronger contribution from dative bonding (Ca+)←(CO2-). The atomic orbitals (AOs) of Ca+ that are engaged in the covalent bonds are the 4s AO for the electron-sharing bonds and the 3d AOs for the dative bonds. This is further evidence for the assignment of the heavier alkaline-earth atoms as transition metals rather than main-group elements.

Measurement of Photoionization Cross-Section for the Excited States of Atoms: A Review

A review of experimental studies of the measurement of the photoionization cross-section for the excited states of the alkali atoms, alkaline earth atoms, and rare-gas atoms is presented, with emphasis on using multi-step laser excitation, ionization, and the saturation technique. The dependence of the photoionization cross-section from different intermediate states populated in the first step and ionized in the second step are discussed, including results on the photoionization cross-sections measured above the first ionization threshold. Results based on different polarizations of the exciting and the ionizing dye lasers are also discussed. Examples are provided, illustrating the photoionization cross-sections measured using thermionic diode ion detector, atomic beam apparatus in conjunction with a time-of-flight mass spectrometer and DC/RF glow discharge cell as an optogalvanic detection.