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Lamb-dips of R(0), R(2) and P(2) rovibrational transitions in the (2-0) overtone band of the HD molecule are measured at cryogenic temperatures using the technique of NICE-OHMS spectroscopy. Resulting transition frequencies are $$214\,905\,335\,240\,(100)$$ 214 905 335 240 ( 100 ) kHz for R(0), $$219\,042\,856\,794\,(150)$$ 219 042 856 794 ( 150 ) kHz for R(2) and $$206 \,898 \,802\,150 \,(150)$$ 206 898 802 150 ( 150 ) kHz for P(2). Small, but systematic deviations (at 1.7$$\sigma $$ σ level) are found from advanced ab initio calculations, supporting results from previous studies probing other lines in the (2-0) band. From a combination difference between the R(0) and P(2) lines, an accurate value for rotational-level spacing in the $$v=0$$ v = 0 ground state is determined, of $$\Delta _{(J=2)-(J=0)}= 8\,006\,533\,168\,(26)$$ Δ ( J = 2 ) - ( J = 0 ) = 8 006 533 168 ( 26 ) kHz, well in agreement with theory (at 0.6$$\sigma $$ σ ). Based on the observation of the dispersive line shape of R(0), the status of proposed models for the elusive line shapes of saturated transitions in HD is discussed.

Ro-vibronic spectra of the 13C18O carbon monoxide isotopologue were obtained with (i) emission spectroscopy in the visible region using a Bruker IFS 125HR spectrometer (University of Rzeszów) and (ii) vacuum-ultraviolet absorption spectroscopy using the wave-front-division spectrometer on the DESIRS beamline of the SOLEIL synchrotron. A deperturbation analysis of the 13C18O A1Π(v = 1) level was conducted from 598 observed transitions from the B1Σ+ - A1Π(0, 1), C1Σ+ - A1Π(0, 1), A1Π - X1Σ+(1, 0), B1Σ+ - X1Σ+(0, 0), C1Σ+ - X1Σ+(0, 0), I1Σ– - X1Σ+(2, 0) bands and five further nominally forbidden bands. An effective Hamiltonian and term-value fitting analysis was implemented. Consequently, 135 parameters were floated: 23 molecular parameters, including molecular constants for A1Π(v = 1), I1Σ–(v = 2), d3Δ(v = 6), e3Σ–(v = 3) and D1Δ(v = 1); rotation-electronic (L-uncoupling) mixing of A1Π(v = 1) ∼ [D1Δ(v = 1), I1Σ–(v = 1), I1Σ–(v = 2)] and spin–orbit interaction parameters for A1Π(v = 1) ∼ [d3Δ(v = 6), e3Σ–(v = 3), aʹ3Σ+(v = 11)]; the spin–orbit/spin-electronic/L-uncoupling a3Π(v = 12) ∼ d3Δ(v = 5) and spin–orbit a3Π(v = 12) ∼ [D1Δ(v = 1), I1Σ–(v = 2)] perturbation parameters; as well as 112 ro-vibronic term values of B1Σ+(v = 0) up to J = 50 and C1Σ+(v = 0) up to J = 60. The significant, indirect a3Π(v = 12) ∼ [e3Σ–(v = 2, 3), d3Δ(v = 5, 6)] ∼ A1Π(v = 1) spin–orbit/spin-electronic/L-uncoupling interaction and a3Π(v = 12) ∼ [I1Σ–(v = 2), D1Δ(v = 1)] ∼ A1Π(v = 1) spin–orbit/L-uncoupling interaction were detected and analysed. Thus, this study, using modern experimental methods and deperturbation analysis, leads to a much improved description in terms of molecular constants and interaction parameters, compared to previous studies of the A1Π(v = 1) energy region in the 13C18O isotopologue. This research is a continuation of the studies on the A1Π state and its numerous perturbers in the CO isotopologues made by our team.

We present the results of a joint experimental and theoretical study of plasma expansion arising from Nd:YAG laser ablation (laser wavelength λ = 1.064 μm) of tin microdroplets in the context of extreme ultraviolet lithography. Measurements of the ion energy distribution reveal a near-plateau in the distribution for kinetic energies in the range 0.03-1 keV and a peak near 2 keV followed by a sharp fall-off in the distribution for energies above 2 keV. Charge-state resolved measurements attribute this peak to the existence of peaks centered near 2 keV in the Sn3+-Sn8+ ion energy distributions. To better understand the physical processes governing the shape of the ion energy distribution, we have modelled the laser-droplet interaction and subsequent plasma expansion using two-dimensional radiation hydrodynamic simulations. We find excellent agreement between the simulated ion energy distribution and the measurements both in terms of the shape of the distribution and the absolute number of detected ions. We attribute a peak in the distribution near 2 keV to a quasi-spherical expanding shell formed at early times in the expansion.

Rovibrational quantum states in the X1Σg+ electronic ground state of H2 are prepared in the v = 13 vibrational level up to its highest bound rotational level J = 7, and in the highest bound vibrational level v = 14 (for J = 1) by two-photon photolysis of H2S. These states are laser-excited in a subsequent two-photon scheme into F1Σg+ outer well states, where the assignment of the highest (v,J) states is derived from a comparison of experimentally known levels in F1Σg+, combined with ab initio calculations of X1Σg+ levels. The assignments are further verified by excitation of F1Σg+ population into autoionizing continuum resonances, which are compared with multichannel quantum defect calculations. Precision spectroscopic measurements of the F-X intervals form a test for the ab initio calculations of ground state levels at high vibrational quantum numbers and large internuclear separations, for which agreement is found.

A very precise ratio The value of the ratio of the masses of the proton and the electron has a bearing on the values of other physical constants. This ratio is known to a very high precision. Patra et al. improved this precision even further by measuring particular frequencies in the rovibrational spectrum of the hydrogen deuteride molecular ion (HD + ) (see the Perspective by Hori). To reach this high precision, the researchers placed the HD + molecules in an ion trap and surrounded them by beryllium ions. The cold beryllium ions then helped cool the HD + molecules, making the HD + spectral lines narrow enough that the proton-electron mass ratio could be extracted by comparison with theoretical predictions. Science , this issue p. 1238 ; see also p. 1160

Extreme ultraviolet (EUV) lithography is currently entering high-volume manufacturing to enable the continued miniaturization of semiconductor devices. The required EUV light, at 13.5 nm wavelength, is produced in a hot and dense laser-driven tin plasma. The atomic origins of this light are demonstrably poorly understood. Here we calculate detailed tin opacity spectra using the Los Alamos atomic physics suite ATOMIC and validate these calculations with experimental comparisons. Our key finding is that EUV light largely originates from transitions between multiply-excited states, and not from the singly-excited states decaying to the ground state as is the current paradigm. Moreover, we find that transitions between these multiply-excited states also contribute in the same narrow window around 13.5 nm as those originating from singly-excited states, and this striking property holds over a wide range of charge states. We thus reveal the doubly magic behavior of tin and the origins of the EUV light., Extreme ultraviolet (EUV) light is entering use in nanolithography. Here the authors discuss experimental and theoretical results about the prominent role of multiply-excited states in highly charged tin ions in the mechanism of EUV light emission from laser-produced plasma.

The technique of Noise-Immune Cavity Enhanced Optical Heterodyne Molecular Spectroscopy (NICE-OHMS) is employed to detect rovibrational transitions of (Formula presented.) at wavelengths of 1.4 (Formula presented.) m. This intracavity-saturation approach narrows down the typical Doppler-broadened linewidths of about 600 MHz to the sub-MHz domain. The locking of the spectroscopy laser to a frequency-comb laser and the assessment of collisional and further line broadening effects result in transition frequencies with an absolute uncertainty below 10 kHz. The lines targeted for measurement are selected by the spectroscopic-network-assisted precision spectroscopy (SNAPS) approach. The principal aim is to derive precise and accurate relative energies from a limited set of Doppler-free transitions (Formula presented.). The 71 newly observed lines, combined with further highly accurate literature transitions, allow the determination of the relative energies for all of the 59 rovibrational states up to J = 6 within the (Formula presented.) vibrational parent of (Formula presented.), where J is the overall rotational quantum number and (Formula presented.), (Formula presented.), and (Formula presented.) are quantum numbers associated with the symmetric stretch, bend, and antisymmetric stretch normal modes, respectively. An experimental curiosity of this study is that for strong transitions an apparent signal inversion in the Lamb-dip spectra is observed; a novelty reserved to the NICE-OHMS technique.

A non-linear spectroscopic study of the HDO molecule is performed in the wavelength range of 1.36–1.42 μ m using noise-immune cavity-enhanced optical-heterodyne molecular spectroscopy (NICE-OHMS). More than 100 rovibrational Lamb dips are recorded, with an experimental precision of 2–20 kHz, related to the first overtone of the O–H stretch fundamental of HD16O and HD18O. Significant perturbations, including distortions, shifts, and splittings, have been observed for a number of Lamb dips. These spectral perturbations are traced back to an AC-Stark effect, arising due to the strong laser field applied in all saturation-spectroscopy experiments. The AC-Stark effect mixes parity pairs, that is pairs of rovibrational states whose assignment differs solely in the K c quantum number, where K c is part of the standard J K a , K c asymmetric-top rotational label. Parity-pair mixing seems to be especially large for parity pairs with K a ≥ 3, whereby their energy splittings become as small as a few MHz, resulting in multi-component asymmetric Lamb-dip profiles of gradually increasing complexity. These complex profiles often include crossover resonances. This effect is well known in saturation spectroscopy, but has not been reported in combination with parity-pair mixing. Parity-pair mixing is not seen in H 2 16 O and H 2 18 O, because their parity pairs correspond to ortho and para nuclear-spin isomers, whose interaction is prohibited. Despite the frequency shifts observed for HD16O and HD18O, the absolute accuracy of the detected transitions still exceeds that achievable by Doppler-limited techniques.

Photoabsorption spectra of ${}^{14}{\rm N}{}^{15}{\rm N}$ were recorded at high resolution with a vacuum-ultraviolet Fourier-Transform spectrometer fed by synchrotron radiation in the range 81 to 100 nm. The combination of high column density ($3\times 10^{17}$ cm$^{-2}$) and low temperature (98 K) allowed for the recording of weak spin-forbidden absorption bands exciting levels of triplet character. The triplet states borrow intensity from ${}^1\Pi_u$ states of Rydberg and valence character while causing their predissociation. New predissociation linewidths and molecular constants are obtained for the states $C\,{}^3\Pi_u(v=7,8,14,15,16,21)$, $G\,{}^3\Pi_u(v=0,1,4)$, and $F\,{}^3\Pi_u(v=0)$. The positions and widths of these levels are shown to be well-predicted by a coupled-Schroedinger equation model with empirical parameters based on experimental data on ${}^{14}{\rm N}_2$ and ${}^{15}{\rm N}_2$ triplet levels., Comment: 16 pages, 16 figures

Shape resonances in ${\mathrm{H}}_{2}$, produced as reaction intermediates in the photolysis of ${\mathrm{H}}_{2}\mathrm{S}$ precursor molecules, are measured in a half-collision approach. Before disintegrating into two ground state H atoms, the reaction is quenched by two-photon Doppler-free excitation to the $\mathrm{F}$ electronically excited state of ${\mathrm{H}}_{2}$. For $J=13$, 15, 17, 19, and 21, resonances with lifetimes in the range of nano- to milliseconds were observed with an accuracy of 30 MHz (1.4 mK). The experimental resonance positions are found to be in excellent agreement with theoretical predictions when nonadiabatic and quantum electrodynamical corrections are included. This is the first time such effects are observed in collisions between neutral atoms. From the potential energy curve of the ${\mathrm{H}}_{2}$ molecule, now tested at high accuracy over a wide range of internuclear separations, the $s$-wave scattering length for singlet $\mathrm{H}(1s)+\mathrm{H}(1s)$ scattering is determined at $a={0.2735}_{31}^{39}$ ${a}_{0}$.

We report on the electrostatic trapping of neutral SrF molecules. The molecules are captured from a cryogenic buffer-gas beam source into the moving traps of a 4.5 m long traveling-wave Stark decelerator. The SrF molecules in $X^2\Sigma^+(v=0, N=1)$ state are brought to rest as the velocity of the moving traps is gradually reduced from 190 m/s to zero. The molecules are held for up to 50 ms in multiple electric traps of the decelerator. The trapped packets have a volume (FWHM) of 1 mm$^{3}$ and a velocity spread of 5(1) m/s which corresponds to a temperature of $60(20)$ mK. Our result demonstrates a factor 3 increase in the molecular mass that has been Stark-decelerated and trapped. Heavy molecules (mass$>$100 amu) offer a highly increased sensitivity to probe physics beyond the Standard Model. This work significantly extends the species of neutral molecules of which slow beams can be created for collision studies, precision measurement and trapping experiments.

© 2021 The Author(s)The rotational structure of the A1Π(v = 2) level of 12C18O is re-examined using high-accuracy experimental data comprised of 541 molecular lines obtained by two complementary Fourier-transform techniques. The absorption spectrum of the A1Π – X1Σ+(2, 0) band, in the range 66,500 - 67,650 cm–1, was recorded by the vacuum-ultraviolet FT spectrometer at the DESIRS beamline of the SOLEIL synchrotron. Visible emission spectra of the B1Σ+ – A1Π(0, 2) and C1Σ+ – A1Π(0, 2) bands in the range 19,200 - 20,000 and 24,300 - 24,800 cm–1 were obtained with a Bruker IFS-125HR spectrometer at the University of Rzeszow. The absolute accuracy of line frequencies are 0.01 and 0.005 - 0.01 cm−1, respectively. Results from the B1Σ+ – X1Σ+(0, 0) and C1Σ+ – X1Σ+(0, 0) absorption bands of 12C18O were added to the experimental data set. A deperturbation analysis of A1Π(v = 2) is performed with an effective Hamiltonian and a term-value fitting approach. Accurate molecular constants for A1Π(v = 2) and the e3Σ–(v = 4), d3Δ(v = 7), aʹ3Σ+(v = 12) and I1Σ–(v = 3) perturbing levels were determined. Perturbation parameters of the spin-orbit A1Π(v = 2) ~ [e3Σ–(v = 4), d3Δ(v = 7), aʹ3Σ+(v = 12)] and rotation-electronic (L-uncoupling) A1Π(v = 2) ~ [I1Σ–(v = 3, 4), D1Δ(v = 3)] interactions, were obtained. A significant, indirect influence of the a3Π state on the A1Π state was detected in 12C18O and has therefore been included in the final fit by taking into account the simultaneous a3Π(v = 13) ~ [e3Σ–(v = 4), d3Δ(v = 7), aʹ3Σ+(v = 12)] ~ A1Π(v = 2) spin-orbit/spin-electronic/L-uncoupling and spin-orbit interactions as well as the a3Π(v = 13) ~ [D1Δ(v = 3), I1Σ–(v = 3)] ~ A1Π(v = 2) spin-orbit and L-uncoupling interactions. This work results in determination of 110 rotational term-values for the A1Π(v = 2) state and its perturbers.

Huge efforts have recently been taken in the derivation of accurate compilations of rovibrational energies of water, one of the most important reference systems in spectroscopy. Such precision is desirable for all water isotopologues, although their investigation is challenged by hyperfine effects in their spectra. Frequency-comb locked noise-immune cavity-enhanced optical-heterodyne molecular spectroscopy (NICE-OHMS) allows for achieving high sensitivity, resolution, and accuracy. This technique has been employed to resolve the subtle hyperfine splittings of rovibrational transitions of H217O in the near-infrared region. Simulation and interpretation of the H217O saturation spectra have been supported by coupled-cluster calculations performed with large basis sets and accounting for high-level corrections. Experimental17O hyperfine parameters are found in excellent agreement with the corresponding computed values. The need of including small hyperfine effects in the analysis of H217O spectra has been demonstrated together with the ability of the computational strategy employed for providing quantitative predictions of the corresponding parameters.

The emission properties of tin plasmas, produced by the irradiation of preformed liquid tin targets by several-ns-long 2 µm-wavelength laser pulses, are studied in the extreme ultraviolet (EUV) regime. In a two-pulse scheme, a pre-pulse laser is first used to deform tin microdroplets into thin, extended disks before the main (2 µm) pulse creates the EUV-emitting plasma. Irradiating 30- to 300 µm-diameter targets with 2 µm laser pulses, we find that the efficiency in creating EUV light around 13.5 nm follows the fraction of laser light that overlaps with the target. Next, the effects of a change in 2 µm drive laser intensity (0.6–1.8 × 1011 W cm−2) and pulse duration (3.7–7.4 ns) are studied. It is found that the angular dependence of the emission of light within a 2% bandwidth around 13.5 nm and within the backward 2π hemisphere around the incoming laser beam is almost independent of intensity and duration of the 2 µm drive laser. With increasing target diameter, the emission in this 2% bandwidth becomes increasingly anisotropic, with a greater fraction of light being emitted into the hemisphere of the incoming laser beam. For direct comparison, a similar set of experiments is performed with a 1 µm-wavelength drive laser. Emission spectra, recorded in a 5.5–25.5 nm wavelength range, show significant self-absorption of light around 13.5 nm in the 1 µm case, while in the 2 µm case only an opacity-related broadening of the spectral feature at 13.5 nm is observed. This work demonstrates the enhanced capabilities and performance of 2 µm-driven plasmas produced from disk targets when compared to 1 µm-driven plasmas, providing strong motivation for the use of 2 µm lasers as drive lasers in future high-power sources of EUV light.

Methanol is an important tracer to probe physical and chemical conditions in the interstellar medium of galaxies. Methanol is also the most sensitive target molecule for probing potential space-time variations of the proton-electron mass ratio, mu, a dimensionless constant of nature. We present an extensive ALMA study of the strongest submillimeter absorption lines of methanol [...] in the z=0.89 molecular absorber toward PKS1830-211, the only high-redshift object in which methanol has been detected. Our goals are to constrain the excitation of the methanol lines and to investigate the cosmological invariance of mu based on their relative kinematics. [...] We explore methanol excitation by running the non local thermal equilibrium radiative transfer code RADEX [...] The excitation analysis points to a cool (~10-20 K) and dense (~10^{4-5} cm-3) methanol gas. [...] In addition, we measure an abundance ratio A/E = 1.0 +/- 0.1, an abundance ratio CH3OH/H2 ~ 2 x 10^{-8}, and a 12CH3OH/13CH3OH ratio 62 +/- 3. Our analysis shows that the bulk velocities of the different transitions are primarily correlated with the observing epoch due to morphological changes in the background quasar's emission. There is a weaker correlation between bulk velocities and the lower level energies of the transitions, which could be a signature of temperature-velocity gradients in the absorbing gas. As a result, we do not find evidence for variations of mu, and we estimate Dmu/mu = (-1.8 +/- 1.2) x 10^{-7} at 1sigma from our multivariate linear regression. We set a robust upper limit | \Dmu/mu | < 3.6 x 10^{-7} (3sigma) for the invariance of mu at a look-back time of half the present age of the Universe. Our analysis highlights that systematics need to be carefully taken into account in future radio molecular absorption studies aimed at testing Dmu/mu below the 10^{-7} horizon. (Abridged), Accepted for publication in A&A

© 2021 Author(s).Taking advantage of the extreme absolute accuracy, sensitivity, and resolution of noise-immune-cavity-enhanced optical-heterodyne-molecular spectroscopy (NICE-OHMS), a variant of frequency-comb-assisted Lamb-dip saturation-spectroscopy techniques, the rotational quantum-level structure of both nuclear-spin isomers of H218O is established with an average accuracy of 2.5 kHz. Altogether, 195 carefully selected rovibrational transitions are probed. The ultrahigh sensitivity of NICE-OHMS permits the observation of lines with room-temperature absorption intensities as low as 10−27 cm molecule−1, while the superb resolution enables the detection of a doublet with a separation of only 286(17) kHz. While the NICE-OHMS experiments are performed in the near-infrared window of 7000-7350 cm−1, the lines observed allow the determination of all the pure rotational energies of H218O corresponding to J values up to 8, where J is the total rotational quantum number. Both network and quantum theory have been employed to facilitate the measurement campaign and the full exploitation of the lines resolved. For example, to minimize the experimental effort, the transitions targeted for observation were selected via the spectroscopic-network-assisted precision spectroscopy (SNAPS) scheme built upon the extended Ritz principle, the theory of spectroscopic networks, and an underlying dataset of quantum chemical origin. To ensure the overall connection of the ultraprecise rovibrational lines for both nuclear-spin isomers of H218O, the NICE-OHMS transitions are augmented with six accurate microwave lines taken from the literature. To produce absolute ortho-H218O energies, the lowest ortho energy is determined to be 23.754 904 61(19) cm−1. A reference, benchmark-quality line list of 1546 transitions, deduced from the ultrahigh-accuracy energy values determined in this study, provides calibration standards for future high-resolution spectroscopic experiments between 0-1250 and 5900-8380 cm−1

Nuclear-spin-symmetry conservation makes the observation of transitions between quantum states of ortho- and para-H_{2} extremely challenging. Consequently, the energy-level structure of H_{2} derived from experiment consists of two disjoint sets of level energies, one for para-H_{2} and the other for ortho-H_{2}. We use a new measurement of the ionization energy of para-H_{2} [E_{I}(H_{2})/(hc)=124 417.491 098(31) cm^{-1}] to determine the energy separation [118.486 770(50) cm^{-1}] between the ground states of para- and ortho-H_{2} and thus link the energy-level structure of the two nuclear-spin isomers of this fundamental molecule. Comparison with recent theoretical results [M. Puchalski et al., Phys. Rev. Lett. 122, 103003 (2019)PRLTAO0031-900710.1103/PhysRevLett.122.103003] enables the derivation of an upper bound of 1.5 MHz for a hypothetical global shift of the energy-level structure of ortho-H_{2} with respect to that of para-H_{2}.

Rayleigh-Brillouin light scattering spectra of CO2 at ultraviolet wavelengths are computed from molecular dynamics which depends on intermolecular potentials only. We find excellent agreement with state of the art experimental data. This agreement was reached in a minimal computational box with sides one scattering wavelength long and integrating the classical trajectories over 20 ns. We also find complete consistency with models based on kinetic theory, which take known values of the transport coefficients as input.

Rotationally resolved spectra of the C 2 Σ + -X 2 Π electronic system of the CH radical were measured using cavity ring-down spectroscopy in supersonically expanding, planar hydrocarbon plasma. The experimental conditions allowed the study of highly excited rotational levels starting from vibrationally excited states. Here we present some 200+ new or more accurately recorded transitions in the 0–0, 1–1 and 2–2 vibronic bands in the ultraviolet between 30900 and 32400 cm −1 (324–309 nm). The resulting data, compared to earlier measurements, allows for the determination of more precise molecular constants for each vibrational state and therefore more precise equilibrium values. From this an equilibrium bond length of 1.115798(17)Å for the C 2 Σ + state is determined. A comprehensive list with observed transitions for each band has been compiled from all available experimental studies and constraints are placed on the predissociation lifetimes.

A measurement of the magnitude of the electric dipole moment of the electron (eEDM) larger than that predicted by the Standard Model (SM) of particle physics is expected to have a huge impact on the search for physics beyond the SM. Polar diatomic molecules containing heavy elements experience enhanced sensitivity to parity (P) and time-reversal (T)-violating phenomena, such as the eEDM and the scalar-pseudoscalar (S-PS) interaction between the nucleons and the electrons, and are thus promising candidates for measurements. The NL-eEDM collaboration is preparing an experiment to measure the eEDM and S-PS interaction in a slow beam of cold BaF molecules [P. Aggarwal et al., Eur. Phys. J. D 72, 197 (2018)]. Accurate knowledge of the electronic structure parameters, Wd and Ws, connecting the eEDM and the S-PS interaction to the measurable energy shifts is crucial for the interpretation of these measurements. In this work, we use the finite field relativistic coupled cluster approach to calculate the Wd and Ws parameters in the ground state of the BaF molecule. Special attention was paid to providing a reliable theoretical uncertainty estimate based on investigations of the basis set, electron correlation, relativistic effects, and geometry. Our recommended values of the two parameters, including conservative uncertainty estimates, are 3.13 ±0.12×1024Hzecm for Wd and 8.29 ± 0.12 kHz for Ws

Experimental spectroscopic studies are presented, in a 5.5-25.5 nm extreme-ultraviolet (EUV) wavelength range, of the light emitted from plasma produced by the irradiation of tin microdroplets by 5-ns-pulsed, 2-mu m-wavelength laser light. Emission spectra are compared to those obtained from plasma driven by 1-mu m-wavelength laser light over a range of laser intensities spanning approximately (0.3-5) x 10(11) W/cm(2), under otherwise identical conditions. Over this range of drive laser intensities, we find that similar spectra and underlying plasma charge state distributions are obtained when keeping the ratio of 1- to 2-mu m laser intensities fixed at a value of 2.1(6), which is in good agreement with RALEF-2D radiation-hydrodynamic simulations. Our experimental findings, supported by the simulations, indicate an approximately inversely proportional scaling similar to lambda(-1) of the relevant plasma electron density, and of the aforementioned required drive laser intensities, with drive laser wavelength lambda. This scaling also extends to the optical depth that is captured in the observed changes in spectra over a range of droplet diameters spanning 16-51 mu m at a constant laser intensity that maximizes the emission in a 2% bandwidth around 13.5 nm relative to the total spectral energy, the bandwidth relevant for EUV lithography. The significant improvement of the spectral performance of the 2-mu m- versus 1-mu m driven plasma provides strong motivation for the development of high-power, high-energy near-infrared lasers to enable the development of more efficient and powerful sources of EUV light.

A supersonic beam source for SrF and BaF molecules is constructed by combining the expansion of carrier gas (a mixture of 2% SF6 and 98% argon) from an Even-Lavie valve with laser ablation of a barium/strontium metal target at a repetition rate of 10 Hz. Molecular beams with a narrow translational velocity spread are produced at relative values of Δv/v = 0.053(11) and 0.054(9) for SrF and BaF, respectively. The relative velocity spread of the beams produced in our source is lower in comparison with the results from other metal fluoride beams produced in supersonic laser ablation sources. The rotational temperature of BaF is measured to be 3.5 K. The source produces 6 × 108 and 107 molecules per steradian per pulse in the X2ς+ (ν = 0, N = 1) state of BaF and SrF molecules, respectively, a state amenable to Stark deceleration and laser cooling.

The spectral distribution of light scattered by microscopic thermal fluctuations in binary mixture gases was investigated experimentally and theoretically. Measurements of Rayleigh-Brillouin spectral profiles were performed at a wavelength of 532 nm and at room temperature, for mixtures of ${\mathrm{SF}}_{6}\text{\ensuremath{-}}\mathrm{He},\phantom{\rule{0.16em}{0ex}}{\mathrm{SF}}_{6}\text{\ensuremath{-}}{\mathrm{D}}_{2}$, and ${\mathrm{SF}}_{6}\text{\ensuremath{-}}{\mathrm{H}}_{2}$. In these measurements, the pressure of the gases with heavy molecular mass $({\mathrm{SF}}_{6})$ is set at 1 bar, while the pressure of the lighter collision partner was varied. In view of the large polarizability of ${\mathrm{SF}}_{6}$ and the very small polarizabilities of He, ${\mathrm{H}}_{2}$, and ${\mathrm{D}}_{2}$, under the chosen pressure conditions these low mass species act as spectators and do not contribute to the light scattering spectrum, while they influence the motion and relaxation of the heavy ${\mathrm{SF}}_{6}$ molecules. A generalized hydrodynamic model was developed that should be applicable for the particular case of molecules with heavy and light disparate masses, as is the case for the heavy ${\mathrm{SF}}_{6}$ molecule, and the lighter collision partners. Based on the kinetic theory of gases, our model replaces the classical Navier-Stokes-Fourier relations with constitutive equations having an exponential memory kernel. The energy exchange between translational and internal modes of motion is included and quantified with a single parameter $z$ that characterizes the ratio between the mean elastic and inelastic molecular collision frequencies. The model is compared with the experimental Rayleigh-Brillouin scattering data, where the value of the parameter $z$ is determined in a least-squares procedure. Where very good agreement is found between experiment and the generalized hydrodynamic model, the computations in the framework of classical hydrodynamics strongly deviate. Only in the hydrodynamic regime both models are shown to converge.

International audience; We present a parts-per-million test of quantum electrodynamics (QED) in the HD+ molecular hydrogen ion, improving on previous tests based on vibrational and rotational transitions by factors of 76 and 1.4, respectively. The test is performed following a unified statistical approach that also produces improved constraints on physics beyond the standard model. We furthermore show how individual constraints derived from the various degrees of freedom in HD+ and antiprotonic helium can be combined to enhance the sensitivity, thus ruling out “fifth forces” on the Ångstrom scale that are 1011 times weaker than the electromagnetic interaction.

Spontaneous Rayleigh-Brillouin (RB) scattering experiments have been performed in air for pressures in the range 0.25–3 bar and temperatures in the range 273–333 K. The functional behaviour of the RB-spectral profile as a function of experimental parameters, such as the incident wavelength, scattering angle, pressure and temperature is analysed, as well as the dependence on thermodynamic properties of the gas, as the shear viscosity, the thermal conductivity, the internal heat capacity and the bulk viscosity. Measurements are performed in a scattering geometry detecting at a scattering angle (Formula presented.) and an incident wavelength of (Formula presented.), at which the Brillouin features become more pronounced than in a right angles geometry and for ultraviolet light. For pressure conditions of 1–3 bar the RB-spectra, measured at high signal-to-noise ratio, are compared to Tenti-S6 model calculations and values for the bulk viscosity of air are extracted. Values of (Formula presented.) are found to exhibit a linear dependence on temperature over the measurement interval in the range (Formula presented.). A temperature dependent value is deduced from a collection of experiments to yield: (Formula presented.). These results are implemented in model calculations that were verified for the low pressure conditions (p

Precise measurement of an atomic hydrogen transition resolves the proton size puzzle., Comment: 3 pages, 1 figure

The A1Π(v = 1) level of the 12C18O isotopologue was precisely reinvestigated with two complementary spectroscopic techniques. High resolution B1Σ+ → A1Π(0, 1), (1, 1) and C1Σ+ → A1Π(0, 1) emission bands were recorded in the visible region, 20,700 – 26,100 cm−1, with a 1.71 m Fourier-transform spectrometer (Bruker IFS 125-HR) installed at the University of Rzeszów. The resulting line centre accuracy of isolated and medium to strong lines is 0.005 cm−1. In addition, high-resolution spectra of the A1Π ⟵ X1Σ+(1, 0), B1Σ+⟵ X1Σ+(0, 0) and (1, 0) as well as C1Σ+⟵ X1Σ+(0, 0) bands were recorded between 66,200 and 95,250 cm−1 using the vacuum-ultraviolet Fourier-transform spectrometer installed at the DESIRS beamline of the SOLEIL synchrotron. The wavenumber accuracy for isolated and strong spectral lines is 0.01 cm−1. A data set of 626 spectral lines belonging to seven bands was incorporated into a global deperturbation analysis. Significantly improved deperturbed molecular constants for the A1Π(v = 1), a´3Σ+(v = 10), D1Δ(v = 1), and I1Σ−(v = 2) levels, term values of the B1Σ+(v = 0, 1) and C1Σ+(v = 0) Rydberg states as well as the accompanying spin-orbit and rotation-electronic (L-uncoupling) interaction parameters were obtained. The experimental ro-vibrational term values of the A1Π(v = 1) level and its perturbers were also determined. The mixed composition of interacting states is expressed in terms of their 1Π percentage character.

Emission spectra from multiply-charged Sn5+–Sn10+ ions are recorded from an electron beam ion trap (EBIT) and from laser-produced plasma (LPP) in the extreme ultraviolet range relevant for nanolithographic applications. Features in the wavelength regime between 12.6 and 20.8 nm are studied. Using the Cowan code, emission line features of the charge-state-resolved Sn ion spectra obtained from the EBIT are identified. Emission features from tin LPP either from a liquid micro-droplet or planar solid target are subsequently identified and assigned to specific charge states using the EBIT data. For the planar solid tin target, the 4d–5p transitions of Sn8+–Sn10+ ions are shown to dominate the long-wavelength part of the measured spectrum and transitions of type 4d–4f + 4p–4d are visible in absorption. For the droplet target case, a clear increase in the charge state distribution with increasing laser intensity is observed. This qualitatively demonstrates the potential of using long-wavelength out-of-band emission features to probe the charge states contributing to the strong unresolved transition array at 13.5 nm relevant for nanolithography.

Accurate Fourier-transform spectroscopic absorption measurements of vacuum ultraviolet transitions in atomic nitrogen and carbon were performed at the Soleil synchrotron. For 14N, transitions from the 2s22p34S3/2 ground state and from the 2s22p32P and 2D metastable states were determined in the 95&ndash, 124 nm range at an accuracy of 0.025cm&minus, 1. The combination of these results with data from previous precision laser experiments in the vacuum ultraviolet range reveals an overall and consistent offset of &minus, 0.04 cm&minus, 1 from values reported in the NIST database. The splittings of the 2s22p34S3/2 &ndash, 2s2p44PJ transitions are well-resolved for 14N and 15N and the isotope shifts determined. While excitation of a 2p valence electron yields very small isotope shifts, excitation of a 2s core electron results in large isotope shifts, in agreement with theoretical predictions. For carbon, six transitions from the ground 2s22p23PJ and 2s22p3s3PJ excited states at 165 nm are measured for both 12C and 13C isotopes.

Although the thermal conductivity of molecular gases can be measured straightforwardly and accurately, it is difficult to experimentally determine its separate contributions from the translational and internal motions of gas molecules. Yet, this information is critical in rarefied gas dynamics as the rarefaction effects corresponding to these motions are different. In this paper, we propose a novel methodology to extract the translational thermal conductivity (or equivalently, the translational Eucken factor) of molecular gases from the Rayleigh–Brillouin scattering (RBS) experimental data. From the numerical simulation of the Wu et al. (J. Fluid Mech., vol. 763, 2015, pp. 24–50) model we find that, in the kinetic regime, in addition to bulk viscosity, the RBS spectrum is sensitive to the translational Eucken factor, even when the total thermal conductivity is fixed. Thus it is not only possible to extract the bulk viscosity, but also the translational Eucken factor of molecular gases from RBS light scattering spectra measurements. Such experiments bear the additional advantage that gas–surface interactions do not affect the measurements. By using the Wu et al. model, bulk viscosities (due to the rotational relaxation of gas molecules only) and translational Eucken factors of N2 , CO2 and SF6 are simultaneously extracted from RBS experiments.

The $3p^{4}$ $^{3}$P$_{J}$ - $3p^{3}4p$ $^{3}$P$_{J}$ transition in the sulphur atom is investigated in a precision two-photon excitation scheme under Doppler-free and collision-free circumstances yielding an absolute accuracy of 0.0009 cm$^{-1}$, using a narrowband pulsed laser. This verifies and improves the level separations between amply studied odd parity levels with even parity levels in S I. An improved value for the $^{3}$P$_{2}$ - $^{3}$P$_{1}$ ground state fine structure splitting is determined at $396.0564$ (7) cm$^{-1}$. A $^{34}$S - $^{32}$S atomic isotope shift was measured from combining time-of-flight mass spectrometry with laser spectroscopy., J. Phys. B: At. Mol. Opt. Phys (2020)

Extreme-ultraviolet (EUV) spectra of ${\mathrm{Sn}}^{13+}\ensuremath{-}{\mathrm{Sn}}^{15+}$ ions have been measured in an electron-beam ion trap (EBIT). A matrix inversion method is employed to unravel convoluted spectra from a mixture of charge states typically present in an EBIT. The method is benchmarked against the spectral features of resonance transitions in ${\mathrm{Sn}}^{13+}$ and ${\mathrm{Sn}}^{14+}$ ions. Three new EUV lines in ${\mathrm{Sn}}^{14+}$ confirm its previously established level structure. This ion is relevant for EUV nanolithography plasma but no detailed experimental data currently exist. We used the Cowan code for first line identifications and assignments in ${\mathrm{Sn}}^{15+}$. The collisional-radiative modeling capabilities of the Flexible Atomic Code were used to include line intensities in the identification process. Using the 20 lines identified, we have established 17 level energies of the $4{p}^{4}4d$ configuration as well as the fine-structure splitting of the $4{p}^{5}$ ground-state configuration. Moreover, we provide state-of-the-art ab initio level structure calculations of ${\mathrm{Sn}}^{15+}$ using the configuration-interaction many-body perturbation code ambit. We find that the here-dominant emission features from the ${\mathrm{Sn}}^{15+}$ ion lie in the narrow 2% bandwidth around 13.5 nm that is relevant for plasma light sources for state-of-the-art nanolithography.

Synopsis Highly charged tin ions are the sources of extreme ultraviolet (EUV) light at 13.5-nm wavelength in laser-produced transient plasmas for next-generation nanolithography. Generating this EUV light at the required power, reliability, and stability however presents a formidable task that combines industrial innovations with challenging scientific questions. We will present work on the spectroscopy of tin ions in and out of YAG-laser-driven plasma and present a surprising answer to the key question: what makes that light?

A saturation spectroscopy measurement of the P(1) line of the ($2-0$) band in HD is performed in a sensitive cavity-enhanced optical setup involving frequency comb calibration. The spectral signature is that of a Lamb-peak, in agreement with a density-matrix model description involving 9 hyperfine components and 16 crossover resonances of $\Lambda$-type. Comparison of the experimental spectra with the simulations yields a rovibrational transition frequency at 209,784,242,007 (20) kHz. Agreement is found with a first principles calculation in the framework of non-adiabatic quantum electrodynamics within 2$\sigma$, where the combined uncertainty is fully determined by theory.

The emission spectra from an industrial, droplet-based, laser-produced plasma, extreme ultraviolet light source for nanolithography are here presented and analyzed. The dependence of spectral features on the CO2-drive-laser intensity is studied by changing the beam spot size at constant pulse energy and duration. We characterize the spectrum by fitting the results of atomic structure calculations to the short-wavelength region (7–11 nm), where the contributions from various charge states can be resolved, and obtain the relative contributions of charge states Sn9+ –Sn15+ . These relative contributions are compared to charge state populations as calculated with the non-equilibrium plasma kinetics code flychk. The calculations are shown to be in good qualitative agreement with the results, showing that the effective plasma temperature, and with it, the shape of the unresolved, main emission feature at 13.5 nm, is a remarkably weak function of laser intensity under this source normal operating conditions.

High-resolution coherent Raman spectroscopic measurements of all three tritium-containing molecular hydrogen isotopologues T$_2$, DT and HT were performed to determine the ground electronic state fundamental Q-branch ($v=0 \rightarrow 1, \Delta J = 0$) transition frequencies at accuracies of $0.0005$ cm$^{-1}$. An over hundred-fold improvement in accuracy over previous experiments allows the comparison with the latest ab initio calculations in the framework of Non-Adiabatic Perturbation Theory including nonrelativisitic, relativisitic and QED contributions. Excellent agreement is found between experiment and theory, thus providing a verification of the validity of the NAPT-framework for these tritiated species. While the transition frequencies were corrected for ac-Stark shifts, the contributions of non-resonant background as well as quantum interference effects between resonant features in the nonlinear spectroscopy were quantitatively investigated, also leading to corrections to the transition frequencies. Methods of saturated CARS with the observation of Lamb dips, as well as the use of continuous-wave radiation for the Stokes frequency were explored, that might pave the way for future higher-accuracy CARS measurements., Comment: 15 pages, 13 figures

The status of searches for possible variation in the constants of nature from astronomical observation of molecules is reviewed, focusing on the dimensionless constant representing the proton-electron mass ratio $\mu=m_p/m_e$. The optical detection of H$_2$ and CO molecules with large ground-based telescopes (as the ESO-VLT and the Keck telescopes), as well as the detection of H$_2$ with the Cosmic Origins Spectrograph aboard the Hubble Space Telescope is discussed in the context of varying constants, and in connection to different theoretical scenarios. Radio astronomy provides an alternative search strategy bearing the advantage that molecules as NH$_3$ (ammonia) and CH$_3$OH (methanol) can be used, which are much more sensitive to a varying $\mu$ than diatomic molecules. Current constraints are $|\Delta\mu/\mu| < 5 \times 10^{-6}$ for redshift $z=2.0-4.2$, corresponding to look-back times of 10-12.5 Gyrs, and $|\Delta\mu/\mu| < 1.5 \times 10^{-7}$ for $z=0.88$, corresponding to half the age of the Universe (both at 3$\sigma$ statistical significance). Existing bottlenecks and prospects for future improvement with novel instrumentation are discussed., Comment: Contribution to Workshop "High Performance Clocks in Space" at the International Space Science Institute, Bern 2015

High signal-to-noise and high-resolution light scattering spectra are measured for nitrous oxide (N2O) gas at an incident wavelength of 403.00 nm, at 90° scattering, at room temperature and at gas pressures in the range 0.5−4 bar. The resulting Rayleigh–Brillouin light scattering spectra are compared to a number of models describing in an approximate manner the collisional dynamics and energy transfer in this gaseous medium of this polyatomic molecular species. The Tenti-S6 model, based on macroscopic gas transport coefficients, reproduces the scattering profiles in the entire pressure range at less than 2% deviation at a similar level as does the alternative kinetic Grad's 6-moment model, which is based on the internal collisional relaxation as a decisive parameter. A hydrodynamic model fails to reproduce experimental spectra for the low pressures of 0.5-1 bar, but yields very good agreement (< 1%) in the pressure range 2−4 bar. While these three models have a different physical basis the internal molecular relaxation derived can for all three be described in terms of a bulk viscosity of ηb∼(6±2)×10−5 Pa · s. A ‘rough-sphere’ model, previously shown to be effective to describe light scattering in SF6 gas, is not found to be suitable, likely in view of the non-sphericity and asymmetry of the N-N-O structured linear polyatomic molecule.

Over a thousand spectral lines in the photoexcitation spectrum of molecular deuterium (D2) to np 1 Σ u + and 1 Π u + Rydberg levels ( n ⩾ 4 ) were measured for rotational levels N ′ = 1 –6 in the 117 000–137 000 cm−1 spectral range by two different types of experiments at two synchrotron radiation sources: a vacuum ultraviolet (VUV) Fourier-transform (FT) spectrometer at SOLEIL, Paris and a 10 m-normal-incidence monochromator (NIM) at BESSY II, Berlin. The experimental energies, the absorption cross sections, Einstein A-coefficients, and line widths are compared with ab initio multi-channel quantum defect (MQDT) calculations for these levels. More than 350 R(0) or P(2) lines were assigned, some 280 R(1) or P(3) lines, some 270 R(2) or P(4) lines, over 100 R(3) or P(5) lines, over 90 R(4) lines, and 24 R(5) lines to extract information on the N ′ = 1 –6 excited levels. Transition energies were determined up to excitation energies of 137 000 cm−1 above the ground state, thereby extending earlier work by various authors and considerably improving the spectral accuracy ( 0.1 cm−1), leading to several reassignments. The absorption and the dissociation, ionization and fluorescence excitation cross sections from the NIM experiment are measured on absolute scale and are used to calibrate intensities in the VUV-FT spectra. The overall agreement between experiment and first principles calculations, without adjustable parameters, is excellent in view of the multi-state interferences treated within the MQDT-framework: For the low N ′ values the averaged deviations between those observed in the FT-SOLEIL spectra and those calculated with MQDT are ∼ 0.1 cm−1 with a spread of ∼ 0.5 cm−1. The line intensities in terms of Einstein coefficients are well represented in the MQDT-framework, as are the level widths representing the lifetimes associated with the sum of the three decay channels. These line intensities follow, in general, the 1 / n 3 scaling behavior as characteristic in Rydberg series, but deviations occur and those are explained by MQDT. The decay dynamics of the excited N Rydberg levels is analyzed on the basis of the measured quantum yields for ionization, dissociation and fluorescence observed in the NIM experiment in terms of absolute cross sections for the distinctive channels. In particular in the n = 4 manifolds dissociation is found to play a major role, where in the n = 5 manifolds the behavior is most erratic due to strong competition between decay channels. At n = 6 , ionization takes over as the dominant channel. Despite the excellent agreement between observations and the outcome of the MQDT calculations for both level energies and dynamics, some pronounced deviations are found as in the splitting of the 5 p π , v = 4 –6, N ′ = 1 levels. The shortcomings of the MQDT calculations are ascribed to the treatment of the excited states in terms of a 1 snp single electron configuration, therewith neglecting possible interferences with 1 snf or 2 s core excited states. Some 27 lines remained unassigned; in view of their observation in fluorescence it is stipulated that these lines probe levels in the nf manifold.

The high-resolution B$^1\Sigma^+$ - A$^1\Pi$ (0, 0) and (0, 3) emission bands of the less-abundant $^{13}$C$^{17}$O isotopologue have been investigated by Fourier-transform spectroscopy in the visible region using a Bruker IFS 125HR spectrometer at an accuracy 0.003 cm$^{-1}$. These spectra are combined with high-resolution photoabsorption measurements of the $^{13}$C$^{17}$O B$^1\Sigma^+$ $\leftarrow$ X$^1\Sigma^+$ (0, 0), B$^1\Sigma^+$ $\leftarrow$ X$^1\Sigma^+$ (1, 0) and C$^1\Sigma^+$ $\leftarrow$ X$^1\Sigma^+$ (0, 0) bands recorded with an accuracy of 0.01 cm$^{-1}$ using the vacuum ultraviolet Fourier-transform spectrometer, installed on the DESIRS beamline at the SOLEIL synchrotron. In the studied 17,950 - 22,500 cm$^{-1}$ and 86,800 - 92,100 cm$^{-1}$ regions, 480 transitions have been measured. These new experimental data were combined with data from the C $\to$ A and B $\to$ A systems, previously analyzed in 13C17O. The frequencies of 1003 transitions derived from 12 bands were used to analyze the perturbations between the A$^1\Pi$ ($\nu$ = 0 - 3) levels and rovibrational levels of the d$^3\Delta_i$, e$^3\Sigma^-$, a$'{}^3\Sigma^+$, I$^1\Sigma^-$ and D$^1\Delta$ states as well as to a preliminary investigation of weak irregularities that appear in the B$^1\Sigma^+$ ($\nu$ = 0) level. Deperturbed molecular constants and term values of the A$^1\Pi$ state were obtained. The spin-orbit and L-uncoupling interaction parameters as well as isotopologue-independent spin-orbit and rotation-electronic perturbation parameters were derived., Comment: 37 pages, 8 tables, 7 figures, 91 references