Electronic Spectroscopy of Jet-Cooled NdO.

Chemi-ionization reactions of the type M + O → MO+ + e- (M = Nd or Sm) are currently being investigated as a method to artificially increase the electron density in the ionosphere for control of micro- and radio wave propagation. Experiments involving the release of atomic Nd into the upper atmosphere have resulted in the production of a cloud that, on excitation by solar radiation, emits green light. It has been assumed that NdO was the carrier of this emission, but the existing spectroscopic data needed for this attribution is lacking. While the electronic spectrum of NdO has been well-characterized at wavelengths greater than 590 nm, relatively little spectroscopic data exist for emission wavelengths in the blue-green spectral range. In this study, spectra for jet-cooled NdO were recorded over the range 15,500-21,000 cm-1. Rotationally resolved laser induced fluorescence and vibronically resolved dispersed laser-induced fluorescence spectra were recorded, and nine new electronically excited states were identified. The data indicate that the electronic spectrum of NdO has relatively few allowed transitions in the green spectral range, casting doubt on the assignment of the Nd high-altitude release cloud green emission to NdO.

Kinetics of O3 with Ca+ and Its Higher Oxides CaOn+ (n = 1-3) and Updates to a Model of Meteoric Calcium in the Mesosphere and Lower Thermosphere.

The room-temperature rate constants and product branching fractions of CaOn+ (n = 0-3) + O3 are measured using a selected ion flow tube apparatus. Ca+ + O3 produces CaO+ + O2 with k = 9 ± 4 × 10-10 cm3 s-1, within uncertainty equal to the Langevin capture rate constant. This value is significantly larger than several literature values. Most likely, those values were underestimated due to the reformation of Ca+ from the sequential chemistry of higher calcium oxide cations with O3, as explored here. A rate constant of 8 ± 3 × 10-10 cm3 s-1 is recommended. Both CaO+ and CaO2+ react near the capture rate constant with ozone. The CaO+ reaction yields both CaO2+ + O2 (0.80 ± 0.15 branching) and Ca+ + 2O2. Similarly, the CaO2+ reaction yields both CaO3+ + O2 (0.85 ± 0.15 branching) and CaO+ + 2O2. CaO3+ + O3 yield CaO2+ + 2O2 at 2 ± 1 × 10-11 cm3 s-1, about 2% of the capture rate constant. The results are supported using density functional calculations and statistical modeling. In general, CaOn+ + O3 yield CaOn+1+ + O2, the expected oxidation. Some fraction of CaOn+1+ is produced with sufficient internal energy to further dissociate to CaOn-1+ + O2, yielding the same products as the oxidation of O3 by CaOn+. Mesospheric Ca and Ca+ concentrations are modeled as functions of day, latitude, and altitude using the Whole Atmosphere Community Climate Model (WACCM); incorporating the updated rate constants improves agreement with concentrations derived from lidar measurements.

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.

High resolution electronic spectroscopy of uranium mononitride, UN.

The isoelectronic molecules UN and UO+ are known to have Ω = 3.5 and Ω = 4.5 ground states, respectively (where Ω is the unsigned projection of the electronic angular momentum along the internuclear axis). A ligand field theory model has been proposed to account for the difference [Matthew and Morse, J. Chem. Phys. 138, 184303 (2013)]. The ground state of UO+ arises from the U3+(5f3(4I4.5))O2- configuration. Owing to the higher nominal charge of the N3- ligand, the U3+ ion in UN is stabilized by promoting one of the 5f electrons to the more polarizable 7s orbital, reducing the repulsive interaction with the ligand and rendering U3+(5f27s(4H3.5))N3- the lowest energy configuration. In the present work, we have advanced the characterization of the UN ground state through studies of two electronic transitions, [18.35]4.5-X(1)3.5 and [18.63]4.5-X(1)3.5, using sub-Doppler laser excitation techniques with fluorescence detection. Spectra were recorded under field-free conditions and in the presence of static electric or magnetic fields. The ground state electric dipole moment [µ = 4.30(2) D] and magnetic ge-factor [2.160(9)] were determined from these data. These values were both consistent with the 5f27s configurational assignment. Dispersed fluorescence measurements were used to determine vibrational constants for the ground and first electronically excited states. Electric dipole moments and magnetic ge-factors are also reported for the higher-energy electronically excited states.

Near-thermo-neutral electron recombination of titanium oxide ions.

While the dissociative recombination (DR) of ground-state molecular ions with low-energy free electrons is generally known to be exothermic, it has been predicted to be endothermic for a class of transition-metal oxide ions. To understand this unusual case, the electron recombination of titanium oxide ions (TiO+) with electrons has been experimentally investigated using the Cryogenic Storage Ring. In its low radiation field, the TiO+ ions relax internally to low rotational excitation (≲100 K). Under controlled collision energies down to ∼2 meV within the merged electron and ion beam configuration, fragment imaging has been applied to determine the kinetic energy released to Ti and O neutral reaction products. Detailed analysis of the fragment imaging data considering the reactant and product excitation channels reveals an endothermicity for the TiO+ dissociative electron recombination of (+4 ± 10) meV. This result improves the accuracy of the energy balance by a factor of 7 compared to that found indirectly from hitherto known molecular properties. Conversely, the present endothermicity yields improved dissociation energy values for D0(TiO) = (6.824 ± 0.010) eV and D0(TiO+) = (6.832 ± 0.010) eV. All thermochemistry values were compared to new coupled-cluster calculations and found to be in good agreement. Moreover, absolute rate coefficients for the electron recombination of rotationally relaxed ions have been measured, yielding an upper limit of 1 × 10-7 cm3 s-1 for typical conditions of cold astrophysical media. Strong variation of the DR rate with the TiO+ internal excitation is predicted. Furthermore, potential energy curves for TiO+ and TiO have been calculated using a multi-reference configuration interaction method to constrain quantum-dynamical paths driving the observed TiO+ electron recombination.

Electronic Spectroscopy of SmO in the 645 to 670 nm Range.

The associative ionization reaction Sm + O → SmO+ + e- is being investigated as an electron source that could transiently modify high-altitude electron densities via Sm vapor release. Electronic spectra have been obtained from tests where sounding rockets released Sm vapor, but the interpretation of these results has been hampered by the limited laboratory spectral data available for both SmO and SmO+. The present study extends the spectroscopic characterization of SmO in the 645-670 nm range, where the field data show the most prominent molecular emission features. Rotationally resolved excitation spectra, dispersed laser-induced fluorescence spectra, and fluorescence decay lifetimes are reported. The results are consistent with the assignment of a subset of the red-region bands to configurational transitions of the form Sm2+(4f56s)O2- ↔ Sm2+(4f55d)O2-. Analysis of the excited state hyperfine structure supports this configurational description.

Electronic Spectroscopy and Photoionization of LiBe.

LiBe has been the subject of several theoretical investigations and one spectroscopic study. Initially, these efforts were motivated by interest in the intermetallic bond. More recent work has explored the potential for producing LiBe and LiBe+ at ultracold temperatures. In the present study, we have advanced the spectroscopic characterization of several electronic states of LiBe and the ground state of LiBe+. For the neutral molecule, the 12Π, 22Σ+, 32Σ+, and 42Π(3d) states were observed for the first time. Data for the 22Σ+-X2Σ+ transition support a theoretical prediction that this band system is suitable for direct laser cooling. Photoelectron spectroscopy has been used to determine the ionization energy of LiBe and map the low-energy vibrational levels of LiBe+ X1Σ+. Overall, the results validate the predictions of high-level quantum chemistry calculations for both LiBe and LiBe+.

Electronic Spectroscopy and Photoionization of LiMg.

Dimers consisting of an alkali metal bound to an alkaline earth metal are of interest from the perspectives of their bonding characteristics and their potential for being laser cooled to ultracold temperatures. There have been experimental and theoretical studies of many of these species, but spectroscopic data for LiMg and the LiMg+ cation are sparse. In this study, rotationally resolved electronic spectra for LiMg are presented. The ground state is confirmed to be X12Σ+ and observations of low-lying electronically excited states are reported for the first time. Reexamination of transitions in the near-UV spectral range indicates that previous band assignments should be revised. Two-color laser excitation techniques were used to determine an ionization energy of 4.7695(4) eV. This value is 1.2 eV below the previously reported experimental estimate. Vibrationally resolved spectra were obtained for LiMg+, yielding molecular constants that were consistent with a substantial strengthening of the bond on ionization.

Dipole-phonon quantum logic with alkaline-earth monoxide and monosulfide cations.

Dipole-phonon quantum logic (DPQL) leverages the interaction between polar molecular ions and the motional modes of a trapped-ion Coulomb crystal to provide a potentially scalable route to quantum information science. Here, we study a class of candidate molecular ions for DPQL, the cationic alkaline-earth monoxides and monosulfides, which possess suitable structure for DPQL and can be produced in existing atomic ion experiments with little additional complexity. We present calculations of DPQL operations for one of these molecules, CaO+, and discuss progress towards experimental realization. We also further develop the theory of DPQL to include state preparation and measurement and entanglement of multiple molecular ions.

Spectroscopy and electronic structure of the hypermetallic oxide, MgOMg.

Electronic spectra for the hypermetallic oxide MgOMg have been observed in the 21 100 cm-1-24 000 cm-1 spectral range using laser induced fluorescence and two-photon resonantly enhanced ionization techniques. Rotationally resolved data confirmed the prediction of a X̃1Σg + ground state. The spectrum was highly congested due to the optical activity of a low-frequency bending mode and the presence of three isotopologues with significant natural abundances. Ab initio calculations predict a bent equilibrium structure for the Ã1B2 upper state, consistent with the observation of a long progression of the bending vibration mode. However, the vibrational intervals were not reproduced by the theoretical calculations. In part, this discrepancy is attributed to strong vibronic coupling between multiple electronically excited states. Two-photon ionization measurements were used to determine an ionization energy of 6.5800(25) eV.

The electronic structure of thorium monoxide: Ligand field assignment of states in the range 0-5 eV.

Configuration interaction ligand field theory (CI LFT) calculations of the electronic energy levels of ThO were performed by treating the molecular electronic states as Th 2+ free-ion levels perturbed by the ligand field of O2- . Twenty nine experimentally characterized ThO v = 0 energy levels, together with the energy difference between the v = 0 levels of the Y and W states were fitted using a CI LFT model that included Th 2+ 7s 2 , 6d7s, 6d2 , 7s7p, 6d7p, 5f7s, and 7p2 configurations. Predictions from these calculations were used to provide tentative assignments for 171 out of 250 ThO band heads listed by Gatterer et al. ["Molecular Spectra of Metallic Oxides", Specola Vaticana (1957)]. Term energies for 30 electronic states have been determined based on these assignments. Subsequently, the CI LFT model was refined by fitting to a set of 59 electronic term energies. The inclusion of CI effects together with integer valence, atomic-in-molecule, ionic bonding ideas reveals atomic energy level patterns that are multiply replicated in the molecular energy level patterns of six Th 2+ O2- atomic ion configurations (6d7s, 6d2 , 7s7p, 6d7p, 5f7s, and 7p2 ) revealing the underlying atomic ion structure that gives rise to the complex and seemingly erratic unassigned bands reported in the Vatican Atlas. © 2018 Wiley Periodicals, Inc.

Time-dependent simulations of a CW pumped, pulsed DC discharge Ar metastable laser system.

Optically pumped rare gas lasers have the potential for scaling to output powers above the kW level. In these devices, electrical discharges through He/Rg mixtures (Rg = Ne, Ar, Kr and Xe) are used to generate metastable Rg atoms in the 1s5 state. Optical pumping to the 2p9 level, followed by collisional relaxation to 2p10, is then used to produce lasing on the 2p10-1s5 transition. Several computational models have been developed to analyze CW systems using steady-state approximations for the discharge excitation, optical pumping and lasing processes. However, recent experiments show that repetitively pulsed discharges have advantages for producing larger volume, high-pressure discharges. Here we present dynamic simulations of a CW laser that uses pulsed-discharge production of Ar metastables. Time-dependent equations are solved for both the discharge and lasing process. Two models are investigated. The first considers the conditions within the lasing medium to be spatially uniform (zero-dimensional model). The second allows for spatial variations along the lasing axis (one-dimensional model). The models were evaluated by simulating the performance characteristics of an experimentally demonstrated system that provides time-averaged output energies in the range of 3-4 W. Time-dependent species densities, laser power and longitudinal spatial distributions are presented.

Demonstration of a quasi-CW diode-pumped metastable xenon laser.

In this work, we present the first demonstration of a quasi-continuous-wave diode-pumped metastable xenon laser at atmospheric pressures. Lasing in metastable noble gas species has received increased attention in the last few years as a possible high-power laser source. This demonstration shows that metastable xenon has a sufficiently broad absorption spectrum to be pumped with a broad-bandwidth diode laser. This implies that a high-power metastable xenon gas laser should be achievable using high-power pump diodes.

Low energy states of NdO+ probed by photoelectron spectroscopy.

The ionization energy (IE) of NdO and the low-energy electronic states of NdO+ have been examined by means of two-color photoionization spectroscopy. The value obtained for the IE, 5.5083(2) eV, is 0.54 eV higher than previous estimates. This leads to the conclusion that the autoionization reaction Nd + O → NdO+ + e- is exothermic by 1.76(10) eV. Thirty vibronic levels of NdO+ arising from eight electronic states were observed with partial rotational resolution. The energy level pattern and supporting electronic structure calculations indicated that all of the observed states correlated with the Nd3+(4f3, 4I)O2- configuration. The structure was consistent with a ligand field theory model where the electronic states of the Nd3+(4f3, 4I) atomic ion define a repeated motif in the electronic state energy intervals of the molecular ion. Comparisons with UO+ show close similarity in the electronic structures of these isoelectronic species.

Characterization of gas-phase thorium nitride.

Properties of gas-phase thorium nitride, ThN, have been experimentally determined from a combined optical and microwave spectroscopic study. An intense band near 555 nm has been assigned as the [18.0]1.5-X2Σ+ (0,0) transition and recorded at high resolution in the presence of static electric and magnetic fields. The observed optical Stark shifts were analyzed to determine permanent electric dipole moments, µâ†’el for the [18.0]1.5 and X2Σ+ states of 4.38 ± 0.02D and 5.11 ± 0.09D, respectively. Zeeman shifts were used to determine the magnetic g-factors. The pure rotational spectrum was recorded using a separated field optical pump/probe microwave repopulation scheme and analyzed to determine the bond length and 14N magnetic hyperfine and nuclear electric quadrupole parameters. A molecular orbital correlation diagram and ligand field electronic structure models are used to provide a qualitative interpretation of the electronic state ordering, magneto- and electro-static properties, and hyperfine interactions. Electronic structure calculations for the X2Σ+ state were performed, and results were compared with observations. Observed trends in µâ†’el for the ThX (X = N, S, O, F, and Cl) series are discussed.

Computational investigation of energy transfer and line broadening for Ar* + He collisions.

Potential energy curves for all states arising from the interaction of He with the 3p6, 3p54s, and 3p54p configurations of Ar have been determined using high-level electronic structure calculations. The results have been used to examine collisional energy transfer probabilities and spectral line shape parameters (shifting and broadening rate coefficients). The main focus has been on states and transitions that are of relevance to optically pumped He/Ar* laser systems. The line shape predictions were found to be in good agreement with experimental data, while there is notable disagreement for the energy transfer probabilities. The experimental data are found to be at variance with the predictions of standard two-state curve crossing models for energy transfer.

Ab initio interatomic potentials and transport properties of alkali metal (M = Rb and Cs)-rare gas (Rg = He, Ne, Ar, Kr, and Xe) media.

We performed a first principle systematic calculation on the adiabatic potential energy curves (PECs) of alkali metal (M = Rb and Cs) - rare gas (Rg = He, Ne, Ar, Kr, and Xe) van der Waals molecules over a wide range of interatomic distance R. All electron basis sets of triple and quadruple zeta valence quality were used for the He, Ne, Ar and Kr atoms. Scalar relativistic effects were taken into account for the heavy Rb, Cs and Xe atoms by means of Dirac-Fock effective core potentials. The correlated ground state energies have been obtained within the framework of the spin unrestricted open-shell coupled cluster method, with perturbative treatment of triple excitations. The electronic energies were corrected for the basis set superposition error (BSSE) using the counterpoise method. Energies were extrapolated to the complete basis set (CBS) limit using a two-point scheme. The energy convergence towards the CBS limit was monitored by the saturation of the dummy atom basis set that included bond functions centered at the midpoint of the interatomic distance. The ab initio point-wise PEC was followed to small R to the point where the energy was 0.5 Hartree above the dissociation limit. A Morse long-range (MLR, UM Rg(R)) potential possessing the correct asymptotic behavior at R → ∞ was fitted to the single point energies. The resulting set of fully analytical MLR potentials was then used to evaluate classical collision integrals over a wide range of collision energies. By this means, diffusion coefficients (DM Rg(T)) were predicted as functions of the translation temperature T ≤ 3000 K. The reliability of the present ab initio UM Rg(R) and DM Rg(T) functions was accessed through a comparison with previous theoretical and experimental results.

Photoelectron Velocity Map Imaging Spectroscopy of the Beryllium Sulfide Anion, BeS.

Slow electron velocity map imaging (SEVI) spectroscopy was used to examine the BeS- anion to neutral ground-state transition, X 2Σ+ → X 1Σ+. Rotational constants, vibrational intervals, and the electron binding energy of BeS- were determined. Partially resolved rotational contours were seen due to the relatively small moment of inertia of beryllium sulfide. Upon analysis of the rotational contours, it was found that changes in the molecular rotational angular momentum, ΔN = -1, -2, -3, and -4, facilitated photodetachment at near-threshold photon energies. The electron affinity of BeS was found to be 2.3346(2) eV. SEVI spectra recorded using photon energies near the threshold for Δv = -1 processes exhibited features that were associated with a dipole-bound state (DBS) of BeS-. Autodetachment spectroscopy was used to probe this state, and rotationally resolved data were obtained for the DBS 2Σ+, v' = 0 - X 2Σ+, v″ = 0 transition. Analysis of this structure provided the rotational constants for BeS- X, v″ = 0, and the electron binding energy of the DBS. Electronic structure calculations, performed at the RCCSD(T) and MRCI levels of theory, gave predictions that were in good agreement with the experimental observations.

Spectroscopic and theoretical studies of ThCl and ThCl.

The electronic structures of ThCl and ThCl+ have been examined using laser induced fluorescence and two-photon ionization techniques. Rotationally resolved spectra, combined with the predictions from relativistic electronic structure calculations, show that the ground state of the neutral molecule is Th+(7s26d)Cl-, X2Δ3/2. Dispersed fluorescence spectra for ThCl revealed the ground state vibrational levels v = 0-10 and low energy electronic states that also originate from the atomic ion 7s26d configuration. Pulsed field ionization-zero kinetic energy photoelectron spectroscopy established an ionization energy (IE) for ThCl of 51 344(5) cm-1, and the ThCl+ vibrational term energies of the v = 1-3 levels. The zero-point level of the first electronically excited state was found at 949(2) cm-1. Comparisons with high-level theoretical results indicate that the ground and excited states are Th2+(7s6d)Cl- X3Δ1 and Th2+(7s2)Cl- Σ+1, respectively. Relativistic coupled cluster composite thermochemistry calculations yielded an IE within 1.2 kcal/mol of experiment and a bond dissociation energy (118.3 kcal/mol) in perfect agreement with previous experiments.

Photodetachment spectroscopy of the beryllium oxide anion, BeO.

The X2Σ+→X1Σ+ anion to neutral ground state photodetachment of BeO- has been studied by means of photoelectron velocity-map imaging spectroscopy in a newly constructed apparatus. Vibrational intervals, rotational constants, and the electron detachment threshold of BeO- were determined for the first time. The small moment of inertia of beryllium oxide allowed for the observation of partially resolved rotational contours. Analyses of these contours provided evidence of several detachment channels resulting from changes in molecular rotational angular momenta of ΔN = 0, ±1, ±2, and ±3. The relative intensities of these detachment channels were found to be a function of the electron kinetic energy. Experimental results are compared to the predictions of high level ab initio calculations.