Search

An electrostatic hexapole lens is used to manipulate the transverse properties of a beam of barium fluoride molecules from a cryogenic buffer gas source. The spatial distribution of the beam is measured by recording state-selective laser-induced fluorescence on an emccd camera, providing insight into the intensity and transverse position spread of the molecular beam. Although the high mass and unfavorable Stark shift of barium fluoride pose a considerable challenge, the number of molecules in the low-field seeking component of the N=1 state that pass a 4 mm diameter aperture 712 mm behind the source is increased by a factor of 12. Furthermore, it is demonstrated that the molecular beam can be displaced by up to +/-5 mm by moving the hexapole lens. Our measurements agree well with numerical trajectory simulations. We discuss how electrostatic lenses may be used to increase the sensitivity of beam experiments such as the search for the electric dipole moment of the electron.

We demonstrate a novel method to determine the longitudinal phase-space distribution of a cryogenic buffer gas beam of barium-fluoride molecules based on a two-step laser excitation scheme. The spatial resolution is achieved by a transversely aligned laser beam that drives molecules from the ground state $X^2\Sigma^+$ to the $A^2\Pi_{1/2}$ state around 860 nm, while the velocity resolution is obtained by a laser beam that is aligned counter-propagating with respect to the molecular beam and that drives the Doppler shifted $A^2\Pi_{1/2}$ to $D^2\Sigma^+$ transition around 797 nm. Molecules in the $D$-state are detected virtually background-free by recording the fluorescence from the $D-X$ transition at 413 nm. As molecules in the ground state do not absorb light at 797 nm, problems due to due to optical pumping are avoided. Furthermore, as the first step uses a narrow transition, this method can also be applied to molecules with hyperfine structure. The measured phase-space distributions, reconstructed at the source exit, show that the average velocity and velocity spread vary significantly over the duration of the molecular beam pulse. Our method gives valuable insight into the dynamics in the source and helps to reduce the velocity and increase the intensity of cryogenic buffer gas beams. In addition, transition frequencies are reported for the $X-A$ and $X-D$ transitions in barium fluoride with an absolute accuracy below 0.3 MHz., Comment: 7 pages, 6 figures

Precision measurement of anti-protonic Helium provides a test of physical laws., Comment: 2 pages, 1 figure

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

We present an investigation of the performance of the relativistic multi-reference Fock-space coupled cluster (FSCC) method for predicting molecular hyperfine structure (HFS) constants, including a thorough computational study to estimate the associated uncertainties. In particular, we considered the $^{19}$F HFS constant in the ground and excited states of BaF. Due to a larger basis set dependence, the uncertainties on the excited state results (16-85%) were found to be significantly larger than those on the ground state constants ($\sim$2%). The ab initio values were compared to the recent experimental results, and good overall agreement within the theoretical uncertainties was found. This work demonstrates the predictive power of the FSCC method and the reliability of the established uncertainty estimates, which can be crucial in cases where the calculated property cannot be directly compared to experiment.

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-\textit{e}EDM collaboration is preparing an experiment to measure the eEDM and S-PS interaction in a slow beam of cold BaF molecules [Eur. Phys. J. D, 72, 197 (2018)]. Accurate knowledge of the electronic structure parameters, $W_d$ and $W_s$, 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 $W_d$ and $W_s$ 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 $\pm$ $0.12 \times 10^{24}\frac{\text{Hz}}{e\cdot \text{cm}}$ for $W_d$ and 8.29 $\pm$ 0.12 kHz for $W_s$.

Spontaneous Rayleigh-Brillouin scattering (RBS) 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 analyzed, 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 $\theta=55.7^\circ$ and an incident wavelength of $\lambda_i=532.22$ nm, 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 $\eta_b$ are found to exhibit a linear dependence on temperature over the measurement interval in the range $1.0 - 2.0 \times 10^{-5}$ Pa$\cdot$s. A temperature dependent value is deduced from a collection of experiments to yield: $\eta_{\rm b} = (0.86 \times 10^{-5}) + 1.29 \times 10^{-7} \cdot (T - 250)$. These results are implemented in model calculations that were verified for the low pressure conditions ($p < 1$ bar) relevant for the Earth's atmosphere. As a result we demonstrate that the RB-scattering spectral profiles for air under sub-atmospheric conditions can be generated via the Tenti-S6 model, for given gas-phase and detection conditions ($p$, $T$, $\lambda_i$, and $\theta$), and for values for the gas transport coefficients.

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 SF$_6-$He, SF$_6-$D$_2$ and SF$_6-$H$_2$. In these measurements, the pressure of the gases with heavy molecular mass (SF$_6$) is set at 1 bar, while the pressure of the lighter collision partner was varied. In view of the large polarizability of SF$_6$ and the very small polarizabilities of He, H$_2$ and 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 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 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.

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 \cite{LeiJFM2015} 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. For the first time, 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.

Rotationally resolved spectra of the C$^2\Sigma^+$-X$^2\Pi$ 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 30900-32400 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) \r{A} for the C$^2{\Sigma}^+$ 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.

The NL-eEDM collaboration is building an experimental setup to search for the permanent electric dipole moment of the electron in a slow beam of cold barium fluoride molecules [Eur. Phys. J. D, 72, 197 (2018)]. Knowledge of molecular properties of BaF is thus needed to plan the measurements and in particular to determine an optimal laser-cooling scheme. Accurate and reliable theoretical predictions of these properties require incorporation of both high-order correlation and relativistic effects in the calculations. In this work theoretical investigations of the ground and the lowest excited states of BaF and its lighter homologues, CaF and SrF, are carried out in the framework of the relativistic Fock-space coupled cluster (FSCC) and multireference configuration interaction (MRCI) methods. Using the calculated molecular properties, we determine the Franck-Condon factors (FCFs) for the $A^2\Pi_{1/2} \rightarrow X^2\Sigma^{+}_{1/2}$ transition, which was successfully used for cooling CaF and SrF and is now considered for BaF. For all three species, the FCFs are found to be highly diagonal. Calculations are also performed for the $B^2\Sigma^{+}_{1/2} \rightarrow X^2\Sigma^{+}_{1/2}$ transition recently exploited for laser-cooling of CaF; it is shown that this transition is not suitable for laser-cooling of BaF, due to the non-diagonal nature of the FCFs in this system. Special attention is given to the properties of the $A'^2\Delta$ state, which in the case of BaF causes a leak channel, in contrast to CaF and SrF species where this state is energetically above the excited states used in laser-cooling. We also present the dipole moments of the ground and the excited states of the three molecules and the transition dipole moments (TDMs) between the different states., Comment: Minor changes; The following article has been submitted to the Journal of Chemical Physics. After it is published, it will be found at https://publishing.aip.org/resources/librarians/products/journals/

Rayleigh-Brillouin scattering spectra of CO$_2$ were measured at pressures ranging from 0.5 to 4~bar, and temperatures from 257 to 355~K using green laser light (wavelength 532~nm, scattering angle of 55.7$^\circ$). These spectra were compared to two lineshape models, which take the bulk viscosity as a parameter. One model applies to the kinetic regime, i.e. low pressures, while the second model uses the continuum, hydrodynamic approach and takes the rotational relaxation time as a parameter, which translates into the bulk viscosity. We do not find a significant dependence of the bulk viscosity with pressure or temperature. At pressures where both models apply we find a consistent value of the ratio of bulk viscosity over shear viscosity $\eta_b/\eta_s = 0.41 \pm 0.10$. This value is four orders of magnitude smaller than the common value that is based on the damping of ultrasound, and signifies that in light scattering only relaxation of rotational modes matters, while vibrational modes remain 'frozen'., Comment: 10 pages, 6 figures

The dissociation energy of H$_2$ represents a benchmark quantity to test the accuracy of first-principles calculations. We present a new measurement of the energy interval between the EF $^1\Sigma_g^+(v=0,N=1)$ state and the 54p1$_1$ Rydberg state of H$_2$. When combined with previously determined intervals, this new measurement leads to an improved value of the dissociation energy $D_0^{N=1}$ of ortho-H$_2$ that has, for the first time, reached a level of uncertainty that is three times smaller than the contribution of about 1 MHz resulting from the finite size of the proton. The new result of 35999.582834(11) cm$^{-1}$ is in remarkable agreement with the theoretical result of 35999.582820(26) cm$^{-1}$ obtained in calculations including high-order relativistic and quantum electrodynamics corrections, as reported in the companion article (M. Puchalski, J. Komasa, P. Czachorowski and K. Pachucki, submitted). This agreement resolves a recent discrepancy between experiment and theory that had hindered a possible use of the dissociation energy of H$_2$ in the context of the current controversy on the charge radius of the proton.

We experimentally demonstrate control over the direction of radiation of a beam that passes through a square nano-aperture in a metal film. The ratio of the aperture size and the wavelength is such that only three guided modes, each with different spatial symmetries, can be excited. Using a spatial light modulator, the superposition of the three modes can be altered, thus allowing for a controlled variation of the radiation pattern that emanates from the nano-aperture. Robust and stable steering of 9.5 degree in two orthogonal directions was achieved.

The cavitation-driven expansion dynamics of liquid tin microdroplets is investigated, set in motion by the ablative impact of a 15-ps laser pulse. We combine high-resolution stroboscopic shadowgraphy with an intuitive fluid dynamic model that includes the onset of fragmentation, and find good agreement between model and experimental data for two different droplet sizes over a wide range of laser pulse energies. The dependence of the initial expansion velocity on these experimental parameters is heuristically captured in a single power law. Further, the obtained late-time mass distributions are shown to be governed by a single parameter. These studies are performed under conditions relevant for plasma light sources for extreme-ultraviolet nanolithography., Comment: 7 pages, 6 figures

We investigate the merits of a measurement of the permanent electric dipole moment of the electron ($e$EDM) with barium monofluoride molecules, thereby searching for phenomena of CP violation beyond those incorporated in the Standard Model of particle physics. Although the BaF molecule has a smaller enhancement factor in terms of the effective electric field than other molecules used in current studies (YbF, ThO and ThF$^+$), we show that a competitive measurement is possible by combining Stark-deceleration, laser-cooling and an intense primary cold source of BaF molecules. With the long coherent interaction times obtainable in a cold beam of BaF, a sensitivity of $5\times10^{-30}$ e$\cdot$cm for an $e$EDM is feasible. We describe the rationale, the challenges and the experimental methods envisioned to achieve this target.

Ion energy distributions arising from laser-produced plasmas of Sn are measured over a wide laser parameter space. Planar-solid as well as liquid-droplet targets are exposed to infrared laser pulses with energy densities between 1J/cm$^2$ and 4kJ/cm$^2$ and durations spanning 0.5ps to 6ns. The measured ion energy distributions are compared to two self-similar solutions of a hydrodynamic approach assuming isothermal expansion of the plasma plume into vacuum. For planar and droplet targets exposed to ps-long pulses we find a good agreement between the experimental results and the self-similar solution of a semi-infinite simple planar plasma configuration with an exponential density profile. The ion energy distributions resulting from solid Sn exposed to ns-pulses agrees with solutions of a limited-mass model that assumes a Gaussian-shaped initial density profile., Comment: contribution to ICPIG 2017

The measurement of the propulsion of metallic microdroplets exposed to nanosecond laser pulses provides an elegant method for probing the ablation pressure in dense laser-produced plasma. We present the measurements of the propulsion velocity over three decades in the driving Nd:YAG laser pulse energy, and observe a near-perfect power law dependence. Simulations performed with the RALEF-2D radiation-hydrodynamic code are shown to be in good agreement with the power law above a specific threshold energy. The simulations highlight the importance of radiative losses which significantly modify the power of the pressure scaling. Having found a good agreement between the experiment and the simulations, we investigate the analytic origins of the obtained power law and conclude that none of the available analytic theories is directly applicable for explaining our power exponent., Comment: 11 pages, 8 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

In 2015, Campbell et al. (Nature 523, 322) presented spectroscopic laboratory gas phase data for the fullerene cation, C$_{60}^+$, that coincide with reported astronomical spectra of two diffuse interstellar band (DIB) features at 9633 and 9578 \AA. In the following year additional laboratory spectra were linked to three other and weaker DIBs at 9428, 9366, and 9349 \AA. The laboratory data were obtained using wavelength-dependent photodissociation spectroscopy of small (up to three) He-tagged C$_{60}^+-$He$_n$ ion complexes, yielding rest wavelengths for the bare C$_{60}^+$ cation by correcting for the He-induced wavelength shifts. Here we present an alternative approach to derive the rest wavelengths of the four most prominent C$_{60}^+$ absorption features, using high resolution laser dissociation spectroscopy of C$_{60}^+$ embedded in ultracold He droplets. Accurate wavelengths of the bare fullerene cation are derived based on linear wavelength shifts recorded for He$_n$C$_{60}^+$ species with $n$ up to 32. A careful analysis of all available data results in precise rest wavelengths (in air) for the four most prominent C$_{60}^+$ bands: 9631.9(1) \AA, 9576.7(1) \AA, 9427.5(1) \AA, and 9364.9(1) \AA. The corresponding band widths have been derived and the relative band intensity ratios are discussed.

Hot white dwarf stars are the ideal probe for a relationship between the fine-structure constant and strong gravitational fields, providing us with an opportunity for a direct observational test. We study a sample of hot white dwarf stars, combining far-UV spectroscopic observations, atomic physics, atmospheric modelling and fundamental physics, in the search for variation in the fine structure constant. This variation manifests as shifts in the observed wavelengths of absorption lines, such as quadruply ionized iron (FeV) and quadruply ionized nickel (NiV), when compared to laboratory wavelengths. Berengut et al. (Phys. Rev. Lett. 2013, 111, 010801) demonstrated the validity of such an analysis using high-resolution Hubble Space Telescope (HST)/Space Telescope Imaging Spectrograph (STIS) spectra of G191-B2B. We have made three important improvements by: (a) using three new independent sets of laboratory wavelengths, (b) analysing a sample of objects, and (c) improving the methodology by incorporating robust techniques from previous studies towards quasars (the Many Multiplet method). A successful detection would be the first direct measurement of a gravitational field effect on a bare constant of nature. Here we describe our approach and present preliminary results from nine objects using both FeV and NiV., Comment: 6 pages, 1 figure, published on 30th March 2017 in Universe as part of VARCOSMOFUN'16 proceedings

Rayleigh-Brillouin spectral profiles are measured with a laser-based scatterometry setup for a 90 degrees scattering angle at a high signal-to-noise ratio (r.m.s. noise below 0.15 \% w.r.t. peak intensity) in sulphur-hexafluoride gas for pressures in the range 0.2 -- 5 bar and for a wavelength of $\lambda=403.0$ nm. The high quality data are compared to a number of light scattering models in order to address the effects of rotational and vibrational relaxation. While the vibrational relaxation rate is so slow that vibration degrees of freedom remain frozen, rotations relax on time scales comparable to those of the density fluctuations. Therefore, the heat capacity, the thermal conductivity and the bulk viscosity are all frequency-dependent transport coefficients. This is relevant for the Tenti model that depends on the values chosen for these transport coefficients. This is not the case for the other two models considered: a kinetic model based on rough-sphere interactions, and a model based on fluctuating hydrodynamics. The deviations with the experiment are similar between the three different models, except for the hydrodynamic model at pressures $p \lesssim 2\;{\rm bar}$. As all models are in line with the ideal gas law, we hypothesize the presence of real gas effects in the measured spectra., Comment: 8 pages, 3 figures, Chemical Physics Letters 2017

The resolution of any spectroscopic or interferometric experiment is ultimately limited by the total time a particle is interrogated. We here demonstrate the first molecular fountain, a development which permits hitherto unattainably long interrogation times with molecules. In our experiments, ammonia molecules are decelerated and cooled using electric fields, launched upwards with a velocity between 1.4 and 1.9\,m/s and observed as they fall back under gravity. A combination of quadrupole lenses and bunching elements is used to shape the beam such that it has a large position spread and a small velocity spread (corresponding to a transverse temperature of $<$10\,$\mu$K and a longitudinal temperature of $<$1\,$\mu$K) when the molecules are in free fall, while being strongly focused at the detection region. The molecules are in free fall for up to 266\,milliseconds, making it possible to perform sub-Hz measurements in molecular systems and paving the way for stringent tests of fundamental physics theories.

Electronic spectra of C$_6$H are measured in the $18\,950-21\,100$ cm$^{-1}$ domain using cavity ring-down spectroscopy of a supersonically expanding hydrocarbon plasma. In total, 19 (sub)bands of C$_6$H are presented, all probing the vibrational manifold of the B$^2\Pi$ electronically excited state. The assignments are guided by electronic spectra available from matrix isolation work, isotopic substitution experiments (yielding also spectra for $^{13}$C$_6$H and C$_6$D), predictions from ab initio calculations as well as rotational fitting and vibrational contour simulations using the available ground state parameters as obtained from microwave experiments. Besides the $0_0^0$ origin band, three non-degenerate stretching vibrations along the linear backbone of the C$_6$H molecule are assigned: the $\nu_6$ mode associated with the C-C bond vibration and the $\nu_4$ and $\nu_3$ modes associated with C$\equiv$C triple bonds. For the two lowest $\nu_{11}$ and $\nu_{10}$ bending modes, a Renner-Teller analysis is performed identifying the $\mu^2\Sigma$($\nu_{11}$) and both $\mu^2\Sigma$($\nu_{10}$) and $\kappa^2\Sigma$($\nu_{10}$) components. In addition, two higher lying bending modes are observed, which are tentatively assigned as $\mu^2\Sigma$($\nu_9$) and $\mu^2\Sigma$($\nu_8$) levels. In the excitation region below the first non-degenerate vibration ($\nu_6$), some $^2\Pi-^{2}\Pi$ transitions are observed that are assigned as even combination modes of low-lying bending vibrations. The same holds for a $^2\Pi-^{2}\Pi$ transition found above the $\nu_6$ level. From these spectroscopic data and the vibronic analysis a comprehensive energy level diagram for the B$^2\Pi$ state of C$_6$H is derived and presented., Comment: Accepted for publication in The Journal of Physical Chemistry A (26 July 2016)

The propulsion of a liquid indium-tin micro-droplet by nanosecond-pulse laser impact is experimentally investigated. We capture the physics of the droplet propulsion in a scaling law that accurately describes the plasma-imparted momentum transfer, enabling the optimization of the laser-droplet coupling. The subsequent deformation of the droplet is described by an analytical model that accounts for the droplet's propulsion velocity and the liquid properties. Comparing our findings to those from vaporization-accelerated mm-sized water droplets, we demonstrate that the hydrodynamic response of laser-impacted droplets is scalable and independent of the propulsion mechanism., Comment: 7 pages, 4 figures

An overview is presented of the H$_2$ quasar absorption method to search for a possible variation of the proton--electron mass ratio $\mu=m_p/m_e$ on a cosmological time scale. Details of the analysis of astronomical spectra, obtained with large 8--10 m class optical telescopes, equipped with high-resolution echelle grating based spectrographs, are explained. The methods and results of the laboratory molecular spectroscopy of H$_2$, in particular the laser-based metrology studies for the determination of rest wavelengths of the Lyman and Werner band absorption lines, are reviewed. Theoretical physics scenarios delivering a rationale for a varying $\mu$ will be discussed briefly, as well as alternative spectroscopic approaches to probe variation of $\mu$, other than the H$_2$ method. Also a recent approach to detect a dependence of the proton-to-electron mass ratio on environmental conditions, such as the presence of strong gravitational fields, will be highlighted. Currently some 56 H$_2$ absorption systems are known and listed. Their usefulness to detect $\mu$-variation is discussed, in terms of column densities and brightness of background quasar sources, along with future observational strategies. The astronomical observations of ten quasar systems analyzed so far set a constraint on a varying proton-electron mass ratio of $|\Delta\mu/\mu| < 5 \times 10^{-6}$ (3-$\sigma$), which is a null result, holding for redshifts in the range $z=2.0-4.2$. This corresponds to look-back times of 10--12.4 billion years into cosmic history. Attempts to interpret the results from these 10 H$_2$ absorbers in terms of a spatial variation of $\mu$ are currently hampered by the small sample size and their coincidental distribution in a relatively narrow band across the sky., Comment: 26 pages, 13 figures, accepted Review of Modern Physics

Spectroscopy of hydrogen can be used for a search into physics beyond the Standard Model. Differences between the absorption spectra of H$_2$ as observed at high redshift and those measured in the laboratory can be interpreted in terms of possible variations of the proton-electron mass ratio. Investigation of some ten of such absorbers in the redshift range $z= 2.0-4.2$ yields a constraint of $|\Delta\mu/\mu|< 5 \times 10^{-6}$ at 3$\sigma$. Observation of H$_2$ from the photospheres of white dwarf stars inside our Galaxy delivers a constraint of similar magnitude on a dependence of $\mu$ on a gravitational potential $10^4$ times as strong as on the Earth's surface. Laser-based precision measurements of dissociation energies, vibrational splittings and rotational level energies in H$_2$ molecules and their deuterated isotopomers HD and D$_2$ produce values for the rovibrational binding energies fully consistent with quantum ab initio calculations including relativistic and quantum electrodynamical (QED) effects. Similarly, precision measurements of high-overtone vibrational transitions of HD$^+$ ions, captured in ion traps and sympathetically cooled to mK temperatures, also result in transition frequencies fully consistent with calculations including QED corrections. Precision measurements of inter-Rydberg transitions in H$_2$ can be extrapolated to yield accurate values for level splittings in the H$_2^+$-ion. These comprehensive results of laboratory precision measurements on neutral and ionic hydrogen molecules can be interpreted to set bounds on the existence of possible fifth forces and of higher dimensions, phenomena describing physics beyond the Standard Model., Comment: Special Review Lecture. Journal of Molecular Spectroscopy

Precise measurements are performed on spectral lineshapes of spontaneous Rayleigh-Brillouin scattering in mixtures of the noble gases Ar and Kr, with He. Admixture of a light He atomic fraction results in marked changes of the spectra, although in all experiments He is merely a spectator atom: it affects the relaxation of density fluctuations of the heavy constituent, but its contribution to the scattered light intensity is negligibly small. The results are compared to a theory for the spectral lineshape without adjustable parameters, yielding excellent agreement for the case of binary mono-atomic gases, signifying a step towards modeling and understanding of light scattering in more complex molecular media.

The rotationally resolved spectrum of the B$^2\Pi-$X$^2\Pi$ electronic origin band transition of $^{13}$C$_6$H is presented. The spectrum is recorded using cavity ring-down spectroscopy in combination with supersonic plasma jets by discharging a $^{13}$C$_2$H$_2$/He/Ar gas mixture. A detailed analysis of more than a hundred fully-resolved transitions allows for an accurate determination of the spectroscopic parameters for both the ground and electronically excited state of $^{13}$C$_6$H., Comment: 4 pages, 1 figure, 2 tables

Spontaneous Rayleigh-Brillouin scattering experiments in air, N2 and O2 have been performed for a wide range of temperatures and pressures at a wavelength of 403 nm and at a 90 degrees scattering angle. Measurements of the Rayleigh-Brillouin spectral scattering profile were conducted at high signal-to-noise ratio for all three species, yielding high-quality spectra unambiguously showing the small differences between scattering in air, and its constituents N2 and O2. Comparison of the experimental spectra with calculations using the Tenti S6 model, developed in 1970s based on linearized kinetic equations for molecular gases, demonstrates that this model is valid to high accuracy. After previous measurements performed at 366 nm, the Tenti S6 model is here verified for a second wavelength of 403 nm. Values for the bulk viscosity for the gases are derived by optimizing the model to the measurements. It is verified that the bulk viscosity parameters obtained from previous experiments at 366 nm, are valid for wavelengths of 403 nm. Also for air, which is treated as a single-component gas with effective gas transport coefficients, the Tenti S6 treatment is validated for 403 nm as for the previously used wavelength of 366 nm, yielding an accurate model description of the scattering profiles for a range of temperatures and pressures, including those of relevance for atmospheric studies. It is concluded that the Tenti S6 model, further verified in the present study, is applicable to LIDAR applications for exploring the wind velocity and the temperature profile distributions of the Earth's atmosphere. Based on the present findings, predictions can be made on the spectral profiles for a typical LIDAR backscatter geometry, which deviate by some 7 percent from purely Gaussian profiles at realistic sub-atmospheric pressures occurring at 3-5 km altitude in the Earth's atmosphere.

Spectra of molecular hydrogen (H$_2$) are employed to search for a possible proton-to-electron mass ratio ($\mu$) dependence on gravity. The Lyman transitions of H$_2$, observed with the Hubble Space Telescope towards white dwarf stars that underwent a gravitational collapse, are compared to accurate laboratory spectra taking into account the high temperature conditions ($T \sim 13\,000$ K) of their photospheres. We derive sensitivity coefficients $K_i$ which define how the individual H$_2$ transitions shift due to $\mu$-dependence. The spectrum of white dwarf star GD133 yields a $\Delta\mu/\mu$ constraint of $(-2.7\pm4.7_{\rm stat}\pm 0.2_{\rm sys})\times10^{-5}$ for a local environment of a gravitational potential $\phi\sim10^4\ \phi_\textrm{Earth}$, while that of G29$-$38 yields $\Delta\mu/\mu=(-5.8\pm3.8_{\rm stat}\pm 0.3_{\rm sys})\times10^{-5}$ for a potential of $2 \times 10^4$ $\phi_\textrm{Earth}$., Comment: 5 pages, 3 figures. Accepted by PRL

The spectral lineshape of spontaneous Rayleigh-Brillouin scattering in CO2 is studied in a range of pressures. The spectrum is influenced by the bulk viscosity, which is a relaxation phenomenon involving the internal degrees of freedom of the molecule. The associated relaxation rates can be compared to the frequency shift of the scattered light, which demands precise measurements of the spectral lineshape. We find the value of the bulk viscosity around 5.7 X 10^{-6} kg/(ms) for the range of pressures p= 2-4 bar and for conditions of room temperature.

Accurate experimental values for the vibrational ground tone or fundamental vibrational energy splitting of H$_2$, HD, and D$_2$ are presented. Absolute accuracies of $2\times10^{-4}$ cm$^{-1}$ are obtained from Doppler-free laser spectroscopy applied in a collisionless environment. The vibrational splitting frequencies are derived from the combination difference between separate electronic excitations from the $X^{1}\Sigma_{g}^{+}, v=0, J$ and $v=1, J$ vibrational states to a common $EF^{1}\Sigma^{+}_{g}, v=0, J$ state. The present work on rotational quantum states $J=1,2$ extends the results reported by Dickenson et al. on $J=0$ [Phys. Rev. Lett. 110 (2013) 193601]. The experimental procedures leading to this high accuracy are discussed in detail. A comparison is made with full \emph{ab initio} calculations encompassing Born-Oppenheimer energies, adiabatic and non-adiabatic corrections, as well as relativistic corrections and QED-contributions. The present agreement between the experimental results and the calculations provides a stringent test on the application of quantum electrodynamics in molecules. Furthermore, the combined experimental-theoretical uncertainty can be interpreted to provide bounds to new interactions beyond the Standard Model of Physics or fifth forces between hadrons., Comment: 14 pages, 10 figures, J. Mol. Spectrosc. (2014) accepted

Photodissociation of 14N2 and 14N15N occurs in interstellar clouds, circumstellar envelopes, protoplanetary discs, and other environments due to UV radiation from stellar sources and the presence of cosmic rays. This source of N atoms initiates the formation of complex N-bearing species and influences their isotopic composition. To study the photodissociation rates of 14N15N by UV continuum radiation and both isotopologues in a field of cosmic ray induced photons. To determine the effect of these on the isotopic composition of more complex molecules. High-resolution photodissociation cross sections of N2 are used from an accurate and comprehensive quantum- mechanical model of the molecule based on laboratory experiments. A similarly high-resolution spectrum of H2 emission following interactions with cosmic rays has been constructed. The spectroscopic data are used to calculate dissociation rates which are input into isotopically differentiated chemical models, describing an interstellar cloud and a protoplanetary disc. The dissociation rate of 14N15N in a Draine field assuming 30K excitation is 1.73x10-10s-1 and the rate due to cosmic rays assuming an H2 ionisation rate of 10-16s-1 is about 10-15s-1, with up to a factor of 10 difference between isotopologues. Shielding functions for 14N15N by 14N2, H2, and H are presented. Incorporating these into an interstellar cloud model, an enhancement of the atomic 15N/14N ratio is obtained due to the self-shielding of external radiation at an extinction of about 1.5 mag. This effect is larger where grain growth has reduced the opacity of dust to ultraviolet radiation. The transfer of photolytic isotopic fractionation N2 to other molecules is significant in a disc model, and is species dependent with 15N enhancement approaching a factor of 10 for HCN.

Transitions in atoms and molecules provide an ideal test ground for constraining or detecting a possible variation of the fundamental constants of nature. In this Perspective, we review molecular species that are of specific interest in the search for a drifting proton-to-electron mass ratio $\mu$. In particular, we outline the procedures that are used to calculate the sensitivity coefficients for transitions in these molecules and discuss current searches. These methods have led to a rate of change in $\mu$ bounded to $6 \times 10^{-14}$/yr from a laboratory experiment performed in the present epoch. On a cosmological time scale the variation is limited to $|\Delta\mu/\mu| < 10^{-5}$ for look-back times of 10-12 billion years and to $|\Delta\mu/\mu| < 10^{-7}$ for look-back times of 7 billion years. The last result, obtained from high-redshift observation of methanol, translates into $\dot{\mu}/\mu = (1.4 \pm 1.4) \times 10^{-17}$/yr if a linear rate of change is assumed., Comment: Accepted Journal of Chemical Physics, 14 Pages, 10 figures

A limit on a possible cosmological variation of the proton-to-electron mass ratio $\mu$ is derived from methanol (CH$_3$OH) absorption lines in the benchmark PKS1830$-$211 lensing galaxy at redshift $z = 0.89$ observed with the Effelsberg 100-m radio telescope, the Institute de Radio Astronomie Millim\'{e}trique 30-m telescope, and the Atacama Large Millimeter/submillimeter Array. Ten different absorption lines of CH$_3$OH covering a wide range of sensitivity coefficients $K_{\mu}$ are used to derive a purely statistical 1-$\sigma$ constraint of $\Delta\mu/\mu = (1.5 \pm 1.5) \times 10^{-7}$ for a lookback time of 7.5 billion years. Systematic effects of chemical segregation, excitation temperature, frequency dependence and time variability of the background source are quantified. A multi-dimensional linear regression analysis leads to a robust constraint of $\Delta\mu/\mu = (-1.0 \pm 0.8_{\rm stat} \pm 1.0_{\rm sys}) \times 10^{-7}$., Comment: 5 pages, 3 figures. Published in PRL

Rovibronic molecular hydrogen (H$_2$) transitions at redshift $z_{\rm abs} \simeq 2.659$ towards the background quasar B0642$-$5038 are examined for a possible cosmological variation in the proton-to-electron mass ratio, $\mu$. We utilise an archival spectrum from the Very Large Telescope/Ultraviolet and Visual Echelle Spectrograph with a signal-to-noise ratio of $\sim$35 per 2.5-km$\,$s$^{-1}$ pixel at the observed H$_2$ wavelengths (335--410 nm). Some 111 H$_2$ transitions in the Lyman and Werner bands have been identified in the damped Lyman $\alpha$ system for which a kinetic gas temperature of $\sim$84 K and a molecular fraction $\log f = -2.18\pm0.08$ is determined. The H$_2$ absorption lines are included in a comprehensive fitting method, which allows us to extract a constraint on a variation of the proton-electron mass ratio, $\Delta\mu/\mu$, from all transitions at once. We obtain $\Delta\mu/\mu = (17.1 \pm 4.5_{\rm stat} \pm3.7_{\rm sys})\times10^{-6}$. However, we find evidence that this measurement has been affected by wavelength miscalibration errors recently identified in UVES. A correction based on observations of objects with solar-like spectra gives a smaller $\Delta\mu/\mu$ value and contributes to a larger systematic uncertainty: $\Delta\mu/\mu = (12.7 \pm 4.5_{\rm stat} \pm4.2_{\rm sys})\times10^{-6}$., Comment: 34 pages, 9 figures. Accepted for publication in ApJ

Rayleigh Brillouin (RB) scattering profiles for air have been recorded for the temperature range from 255 to 340 K and the pressure range from 640 to 3300 mbar, covering the conditions relevant for the Earth's atmosphere and for planned atmospheric light detection and ranging (LIDAR) missions. The measurements performed at a wavelength of 366.8 nm detect spontaneous RB scattering at a 90 degree scattering angle from a sensitive intracavity setup, delivering scattering profiles at a 1 percent rms noise level or better. The elusive transport coefficient, the bulk viscosity, is effectively derived by a comparing the measurements to the model, yielding an increased trend. The calculated (Tenti S6) line shapes are consistent with experimental data at the level of 2 percent, meeting the requirements for the future RB scattering LIDAR missions in the Earth's atmosphere. However, the systematic 2 percent deviation may imply that the model has a limit to describe the finest details of RB scattering in air. Finally, it is demonstrated that the RB scattering data in combination with the Tenti S6 model can be used to retrieve the actual gas temperatures.

Molecular nitrogen is one of the key species in the chemistry of interstellar clouds and protoplanetary disks and the partitioning of nitrogen between N and N2 controls the formation of more complex prebiotic nitrogen-containing species. The aim of this work is to gain a better understanding of the interstellar N2 photodissociation processes based on recent detailed theoretical and experimental work and to provide accurate rates for use in chemical models. We simulated the full high-resolution line-by-line absorption + dissociation spectrum of N2 over the relevant 912-1000 \AA\ wavelength range, by using a quantum-mechanical model which solves the coupled-channels Schr\"odinger equation. The simulated N2 spectra were compared with the absorption spectra of H2, H, CO, and dust to compute photodissociation rates in various radiation fields and shielding functions. The effects of the new rates in interstellar cloud models were illustrated for diffuse and translucent clouds, a dense photon dominated region and a protoplanetary disk., Comment: Online database: http://home.strw.leidenuniv.nl/~ewine/photo

The fundamental ground tone vibration of H2, HD, and D2 is determined to an accuracy of 2 x 10^-4 cm^-1 from Doppler-free laser spectroscopy in the collisionless environment of a molecular beam. This rotationless vibrational splitting is derived from the combination difference between electronic excitation from the X^1Sg+, v=0 and v=1 levels to a common EF^1g+, v=0 level. Agreement within $1\sigma$ between the experimental result and a full ab initio calculation provides a stringent test of quantum electrodynamics in a chemically-bound system., Comment: 5 pages, 3 figures, Phys. Rev. Lett. (2013) accepted

Torsion-rotation transitions in molecules exhibiting hindered internal rotation possess enhanced sensitivities to a variation of the proton-to-electron mass ratio. This enhancement occurs due to a cancellation of energies associated with the torsional and rotational degrees of freedom of the molecule. This effect occurs generally in every internal rotor molecule, but is exceptionally large in methanol. In this paper we calculate the sensitivity coefficients of methyl mercaptan, the thiol analogue of methanol. The obtained sensitivity coefficients in this molecule range from $K_\mu=-14.8$ to $+12.2$ for transitions with a lower-level excitation energy below 10\,cm$^{-1}$.

Values for the bulk viscosity of molecular nitrogen gas (N2) were derived from spontaneous Rayleigh-Brillouin (RB) scattering at ultraviolet wavelengths (366.8 nm) and at a 90 degree scattering angle. Analysis of the scattering profiles yield values showing a linear increasing trend in the temperature interval from 255 K to 340 K. The present values, pertaining to hypersound acoustics at frequencies in the GHz domain, are found to be in agreement with results from acoustic attenuation experiments in N2 performed at MHz frequencies.

Recently, the extremely sensitive torsion-rotation transitions in methanol have been used to set a tight constraint on a possible variation of the proton-to-electron mass ratio over cosmological time scales. In order to improve this constraint, laboratory data of increased accuracy will be required. Here, we explore the possibility for performing high-resolution spectroscopy on methanol in a Stark-deflected molecular beam. We have calculated the Stark shift of the lower rotational levels in the ground torsion-vibrational state of CH3OH and CD3OH molecules, and have used this to simulate trajectories through a typical molecular beam resonance setup. Furthermore, we have determined the efficiency of non-resonant multi-photon ionization of methanol molecules using a femtosecond laser pulse. The described setup is in principle suited to measure microwave transitions in CH3OH at an accuracy below 10^{-8}.