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The intensities of all rovibrational electric quadrupole absorption lines in $^{16}$O$_2$($X^{3}\Sigma^{-}_{g}$), for which the vibrational quantum number is $v \leq 35$ and the total angular momentum quantum number is $J \leq 40$, are calculated in the intermediate coupling using a new $\textit{ab initio}$ quadrupole moment curve of the ground electronic state of O$_2$. The calculated values agree with those available in the HITRAN database, which at present includes only the $1$-$0$ fundamental vibrational band of $^{16}$O$_2$($X^{3}\Sigma^{-}_{g}$). We therefore recommend using the intensities of the vibrational overtones and hot bands reported here in updating the HITRAN database for O$_2$ in the upcoming 2024 edition., Comment: To be submitted to "Journal of Quantitative Spectroscopy & Radiative Transfer"

Measuring low light absorption with combined uncertainty < 1 permille is crucial in a wide range of applications. Popular cavity ring-down spectroscopy can provide ultra-high precision, below 0.01 permille, but its accuracy is strongly dependent on the measurement capabilities of the detection system and typically is about 10 permille. Here, we exploit the optical frequency information carried by the ring-down cavity electromagnetic field, not explored in conventional CRDS, for high-fidelity spectroscopy. Instead of measuring only the decaying light intensity, we perform heterodyne detection of ring-downs followed by Fourier analysis to provide exact frequencies of optical cavity modes and a dispersive spectrum of a gas sample from them. This approach is insensitive to inaccuracies in light intensity measurements and eliminates the problem of detector band nonlinearity, the main cause of measurement error in traditional CRDS. Using the CO and HD line intensities as examples, we demonstrate the sub-permille accuracy of our method, confirmed by the best ab initio results, and the long-term repeatability of our dispersion measurements at 10^(-4) level. Such results have not been achieved in optical spectroscopy before. The high accuracy of the presented method indicates its potential in atmospheric studies, isotope ratio metrology, thermometry, and the establishment of primary gas standards.

We present a rigorous quantum scattering study of the effects of hyperfine and Zeeman interactions on cold Li - H$_{2}$ collisions in the presence of an external magnetic field using a recent ab initio potential energy surface. We find that the low-field-seeking states of H$_{2}$ predominantly undergo elastic collisions: the ratio of elastic-to-inelastic collisions exceeds 100 for collision energies below 1.5 K. Furthermore, we demonstrate that most inelastic collisions conserve the space-fixed projection of the nuclear spin. We show that the anisotropic hyperfine interaction between the nuclear spin of H$_{2}$ and the electron spin of Li can have a significant effect on inelastic scattering in the ultracold regime, as it mediates two processes: the electron spin relaxation in lithium, and the nuclear spin - electron spin exchange. Given the predominance of elastic collisions and the propensity of inelastic collisions to retain H$_{2}$ in its low-field-seeking states, our results open up the possibility of sympathetic cooling of molecular hydrogen by atomic lithium, paving the way for future exploration of ultracold collisions and high-precision spectroscopy of H$_{2}$ molecules., Comment: The following article has been accepted by The Journal of Chemical Physics. After it is published, it will be found at https://pubs.aip.org/aip/jcp

Collisional (de-)excitation of H$_{2}$ by helium plays an important role in the thermal balance and chemistry of various astrophysical environments, making accurate rate coefficients essential for the interpretation of observations of the interstellar medium. Our goal is to utilize a state-of-the-art potential energy surface (PES) to provide comprehensive state-to-state rate coefficients for He-induced transitions among rovibrational levels of H$_{2}$. We perform quantum scattering calculations for the H$_{2}$-He system and provide state-to-state rate coefficients for 1 089 transitions between rovibrational levels of H$_{2}$ with internal energies up to 15 000 cm$^{-1}$ for temperatures ranging from 20 to 8 000 K. Our results show good agreement with previous calculations for pure rotational transitions between low-lying rotational levels, but we find significant discrepancies for rovibrational processes involving highly-excited rotational and vibrational states. We attribute these differences to two key factors: the broader range of intramolecular distances covered by ab initio points, and the superior accuracy of the PES, resulting from the utilization of the state-of-the-art quantum chemistry methods, compared to the previous lower-level calculations. Radiative transfer calculations performed with the new collisional data indicate that the population of rotational levels in excited vibrational states experiences significant modifications, highlighting the critical need for this updated dataset in models of high-temperature astrophysical environments.

The remote sensing of abundance and properties of HCl -- the main atmospheric reservoir of Cl atoms which directly participate in ozone depletion -- are important for monitoring the partitioning of chlorine between "ozone-depleting" and "reservoir" species. Such remote studies require knowledge of the shapes of molecular resonances of HCl, which are perturbed by collisions with the molecules of the surrounding air. In this work, we report the first fully quantum calculations of collisional perturbations of the shape of a pure rotational line in H$^{35}$Cl perturbed by an air-relevant molecule (as the first model system we choose the R(0) line in HCl perturbed by O$_2$). The calculations are performed on our new highly-accurate HCl($X^1\Sigma^+$)-O$_2$($X^3\Sigma^-_g$) potential energy surface. In addition to pressure broadening and shift, we determine also their speed dependencies and the complex Dicke parameter. This gives important input to the community discussion on the physical meaning of the complex Dicke parameter and its relevance for atmospheric spectra (previously, the complex Dicke parameter for such systems was mainly determined from phenomenological fits to experimental spectra and the physical meaning of its value in that context is questionable). We also calculate the temperature dependence of the line-shape parameters and obtain agreement with the available experimental data. We estimate the total combined uncertainties of our calculations at 2% relative RMSE residuals in the simulated line shape at 296~K. This result constitutes an important step towards computational population of spectroscopic databases with accurate ab initio line-shape parameters for molecular systems of terrestrial atmospheric importance., Comment: 15 pages, 7 figures, The following article has been accepted by The Journal of Chemical Physics. After it is published, it will be found at https://pubs.aip.org/aip/jcp

Experiments aimed at searching for variations in the fine-structure constant $\alpha$ are based on spectroscopy of transitions in microscopic bound systems, such as atoms and ions, or resonances in optical cavities. The sensitivities of these systems to variations in $\alpha$ are typically on the order of unity and are fixed for a given system. For heavy atoms, highly charged ions and nuclear transitions, the sensitivity can be increased by benefiting from the relativistic effects and favorable arrangement of quantum states. This article proposes a new method for controlling the sensitivity factor of macroscopic physical systems. Specific concepts of optical cavities with tunable sensitivity to $\alpha$ are described. These systems show qualitatively different properties from those of previous studies of the sensitivity of macroscopic systems to variations in $\alpha$, in which the sensitivity was found to be fixed and fundamentally limited to an order of unity. Although possible experimental constraints attainable with the specific optical cavity arrangements proposed in this article do not yet exceed the present best constraints on $\alpha$ variations, this work paves the way for developing new approaches to searching for variations in the fundamental constants of physics.

The speed-dependent spectral line profiles collapse into a simple Lorentz profile in the regime dominated by the velocity-changing collisions. We derive general formulas for the effective width and shift of the Lorentzian for arbitrary speed-dependent collisional broadening and shift and velocity-changing collision operators. For a quadratic speed dependence of collisional broadening and shift, and the billiard ball model of velocity-changing collisions, we provide simple analytical expressions for the effective Lorentzian width and shift. We show that the effective Lorentzian width and shift split into components originating from the: well-known Dicke-narrowed Doppler width, speed-averaged collisional broadening and shift, their speed dependencies, and a product term that mixes the contributions of the broadening and shift speed dependencies. We show how the components depend on rates of speed-changing and velocity-changing collisions related to the perturber/absorber mass ratio. We validate analytical formulas numerically on example of H$_{2}$ transition perturbed by He., Comment: 12 pages, 3 figures

We report results of a theoretical investigation of hyperfine interactions in two homonuclear isotopologues of the hydrogen molecule: H$_{2}$ and D$_{2}$. We present a set of hyperfine coupling constants: spin-rotation, spin-spin dipole and, in the case of the D$_{2}$ molecule, electric quadrupole coupling constants for all bound states of the two isotopologues in their ground electronic $X^{1}\Sigma^{+}_{g}$ state. We provide a list of positions and intensities of 220 997 hyperfine components of 16 079 rovibrational quadrupole transitions of the O, Q and S branches. The positions and intensities of the hyperfine components are necessary for a reliable interpretation of accurate measurements of rovibrational transition frequencies in H$_{2}$ and D$_{2}$, which are used for tests of the quantum electrodynamics of molecules and searches for new physics beyond the Standard Model.

Stark deceleration enables the production of cold and dense molecular beams with applications in trapping, collisional studies, and precision measurement. Improving the efficiency of Stark deceleration, and hence the achievable molecular densities, is central to unlock the full potential of such studies. One of the chief limitations arises from the transverse focusing properties of Stark decelerators. We introduce a new operation strategy that circumvents this limit without any hardware modifications, and experimentally verify our results for hydroxyl radicals. Notably, improved focusing results in significant gains in molecule yield with increased operating voltage, formerly limited by transverse-longitudinal coupling. At final velocities sufficiently small for trapping, molecule flux improves by a factor of four, and potentially more with increased voltage. The improvement is more significant for less readily polarized species, thereby expanding the class of candidate molecules for Stark deceleration., Comment: 5 pages, 4 figures

Coherent, optically dressed media composed of two-level molecular systems without inversion symmetry are considered as all-optically tunable sources of coherent radiation in the microwave domain. A theoretical model and a numerical toolbox are developed to confirm the main finding: the generation of a low-frequency radiation, and the buildup and propagation dynamics of such low-frequency signals in a medium of polar molecules in a gas phase. The physical mechanism of the signal generation relies on the permanent dipole moment characterizing systems without inversion symmetry. The molecules are polarized with a DC electric field yielding a permanent electric dipole moment in the laboratory frame; the direction and magnitude of the moment depend on the molecular state. As the system is resonantly driven, the dipole moment oscillates at the Rabi frequency and, hence, generates microwave radiation. We demonstrate the tuning capability of the output signal frequency with the drive amplitude and detuning. We find that even though decoherence mechanisms such as spontaneous emission may damp the output field, a scenario based on pulsed illumination yields a coherent, pulsed output of tunable temporal width. Finally, we discuss experimental scenarios exploiting rotational levels of gaseous ensembles of heteronuclear diatomic molecules., Comment: 12 pages, 6 figures

We report on investigations of nonlinear magneto-optical rotation (NMOR) in rubidium vapor subjected to a modulated magnetic field and continuous-wave (CW) laser-light illumination. By superimposing modulation and a static (DC) magnetic field, we demonstrate the appearance of resonances at both small and large (compared to the ground-state relaxation rate) values of the static field. Since in conventional NMOR, there is no rotation at high fields, this suggests an existence of a novel mechanism generating anisotropy in the considered case, which we identify as parametric resonance. The experiments are performed using light of small ellipticity and rotation signals are significantly enhanced by combining atom-induced polarization rotation with a passive rotation induced with a wave plate. All the observations are supported with theoretical simulations. The density-matrix formalism and angular-momentum probability surfaces are used to provide intuitive explanation of the observed signals., Comment: 10 pages, 11 figures

The total mass density of the Universe appears to be dominated by dark matter. However, beyond its gravitational interactions at the galactic scale, little is known about its nature. Extensions of the quantum electrodynamics Lagrangian with dark-matter coupling terms may result in changes to Standard Model parameters. Recently, it was proposed that a network of atomic clocks could be used to search for transient signals of a hypothetical dark matter in the form of stable topological defects. The clocks become desynchronized when a dark-matter object sweeps through the network. This pioneering approach, which is applicable only for distant clocks, is limited by the quality of the fibre links. Here, we present an alternative experimental approach that is applicable to both closely spaced and distant optical atomic clocks and benefits from their individual susceptibilities to dark matter, hence not requiring fibre links. We explore a new dimension of astrophysical observations by constraining the strength of atomic coupling to the hypothetical dark-matter cosmic objects. Our experimental constraint exceeds the previous limits; in fact, it not only reaches the ultimate level expected to be achievable with a constellation of GPS atomic clocks but also has a large potential for improvement.

We report the absolute frequency measurements of rubidium 5S-7S two-photon transitions with a cw laser digitally locked to an atomic transition and referenced to an optical frequency comb. The narrow, two-photon transition, 5S-7S (760 nm) insensitive to first order in a magnetic field, is a promising candidate for frequency reference. The performed tests yield the transition frequency with accuracy better than reported previously., Comment: This paper was published in Optics Letters and is made available as an electronic reprint with the permission of OSA. The paper can be found at http://dx.doi.org/10.1364/OL.38.004581. Systematic or multiple reproduction or distribution to multiple locations via electronic or other means is prohibited and is subject to penalties under law