arXiv subjects

Wim Ubachs

Publications and source records attributed to Wim Ubachs.

At least 55 records · Page 3Linked to original sources

arXiv2014

Precision spectroscopy of the $X\,^{1}Σ_{g}^{+}, v=0\rightarrow 1$ ($J=0-2$) rovibrational splittings in H$_{2}$, HD and D$_{2}$

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 $X^{1}Σ_{g}^{+}, v=0, J$ and $v=1, J$ vibrational states to a common $EF^{1}Σ^{+}_{g}, v=0, J$ 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.

physics.atom-ph↗

arXiv2014

Isotope selective photodissociation of N2 by the interstellar radiation field and cosmic rays

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.

astro-ph.GA↗

arXiv2013

Analysis of Molecular Hydrogen Absorption toward QSO B0642-5038 for a Varying Proton-to-Electron Mass Ratio

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, $μ$. 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 $α$ 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, $Δμ/μ$, from all transitions at once. We obtain $Δμ/μ= (17.1 \pm 4.5_{\rm stat} \pm3.7_{\rm sys})\times10^{-6}$. 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 $Δμ/μ$ value and contributes to a larger systematic uncertainty: $Δμ/μ= (12.7 \pm 4.5_{\rm stat} \pm4.2_{\rm sys})\times10^{-6}$.

astro-ph.CO↗

arXiv2013

Robust Constraint on a Drifting Proton-to-Electron Mass Ratio at z=0.89 from Methanol Observation at Three Radio Telescopes

A limit on a possible cosmological variation of the proton-to-electron mass ratio $μ$ 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 Millimétrique 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 $K_μ$ are used to derive a purely statistical 1-$σ$ constraint of $Δμ/μ= (1.5 \pm 1.5) \times 10^{-7}$ 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 $Δμ/μ= (-1.0 \pm 0.8_{\rm stat} \pm 1.0_{\rm sys}) \times 10^{-7}$.

astro-ph.CO↗

arXiv2013

Perspective: Tipping the scales - search for drifting constants from molecular spectra

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 $μ$. 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 $μ$ 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 $|Δμ/μ| < 10^{-5}$ for look-back times of 10-12 billion years and to $|Δμ/μ| < 10^{-7}$ for look-back times of 7 billion years. The last result, obtained from high-redshift observation of methanol, translates into $\dotμ/μ= (1.4 \pm 1.4) \times 10^{-17}$/yr if a linear rate of change is assumed.

physics.chem-ph↗

arXiv2013

Rayleigh-Brillouin scattering profiles of air at different temperatures and pressures

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.

physics.optics↗

arXiv2013

Photodissociation of interstellar N2

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 Å wavelength range, by using a quantum-mechanical model which solves the coupled-channels Schrödinger 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.

astro-ph.GA↗

arXiv2013

The Fundamental Vibration of Molecular Hydrogen

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 $1σ$ between the experimental result and a full ab initio calculation provides a stringent test of quantum electrodynamics in a chemically-bound system.

physics.atom-ph↗

arXiv2013

Methyl mercaptan (CH3SH) as a probe for $μ$ variation

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 $K_μ=-14.8$ to $+12.2$ for transitions with a lower-level excitation energy below 10\,cm$^{-1}$.

physics.atom-ph↗

arXiv2013

Temperature-dependent bulk viscosity of nitrogen gas determined from spontaneous Rayleigh-Brillouin scattering

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.

physics.optics↗

arXiv2013

Prospects for high-resolution microwave spectroscopy of methanol in a Stark-deflected molecular beam

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}.

physics.atom-ph↗

arXiv2012

A Rayleigh-Brillouin scattering spectrometer for ultraviolet wavelengths

A spectrometer for the measurement of spontaneous Rayleigh-Brillouin scattering line profiles at ultraviolet wavelengths from gas phase molecules has been developed, employing a high-power frequency-stabilized UV laser with narrow bandwidth (2 MHz). The UV light from a frequency-doubled titanium:sapphire laser is further amplified in an enhancement cavity, delivering a 5 Watt UV-beam propagating through the interaction region inside a scattering cell. The design of the RB-scattering cell allows for measurements at gas pressures in the range 0-4 bar and at stably controlled temperatures from -30 to 70 degree Celsius. A scannable Fabry-Perot analyzer with instrument resolution of 232 MHz probes the Rayleigh-Brillouin profiles. Measurements on N2 and SF6 gases demonstrate the high signal-to-noise ratio achievable with the instrument, at the 1% level at the peak amplitude of the scattering profile.

physics.ao-ph↗

arXiv2012

Sensitivity of rotational transitions in CH and CD to a possible variation of fundamental constants

The sensitivity of rotational transitions in CH and CD to a possible variation of fundamental constants has been investigated. Largely enhanced sensitivity coefficients are found for specific transitions which are due to accidental degeneracies between the different fine-structure manifolds. These degeneracies occur when the spin-orbit coupling constant is close to four times the rotational constant. CH and particularly CD match this condition closely. Unfortunately, an analysis of the transition strengths shows that the same condition that leads to an enhanced sensitivity suppresses the transition strength, making these transitions too weak to be of relevance for testing the variation of fundamental constants over cosmological time scales. We propose a test in CH based on the comparison between the rotational transitions between the e and f components of the Omega'=1/2,J=1/2 and Omega'=3/2,J=3/2 levels at 532 and 536 GHz and other rotational or Lambda-doublet transitions in CH involving the same absorbing ground levels. Such a test, to be performed by radioastronomy of highly redshifted objects, is robust against systematic effects.

physics.atom-ph↗

arXiv2012

VUV Fourier-transform absorption study of the Lyman and Werner bands in D2

An extensive survey of the D2 absorption spectrum has been performed with the high-resolution VUV Fourier-transform spectrometer of the DESIRS beamline at the SOLEIL synchrotron. The frequency range of 90 000-119 000 cm-1 covers the full depth of the potential wells of the B 1Σ+u, B' 1Σ+u, and C 1Πu electronic states up to the D(1s) + D(2\ell) dissociation limit. Improved level energies of rovibrational levels have been determined up to respectively v = 51, v = 13, and v = 20. Highest resolution is achieved by probing absorption in a molecular gas jet with slit geometry, as well as in a liquid helium cooled static gas cell, resulting in line widths of ~0.35 cm-1. Extended calibration methods are employed to extract line positions of D2 lines at absolute accuracies of 0.03 cm-1. The D1Πu and B" 1Σ+u electronic states correlate with the D(1s) + D(3\ell) dissociation limit, but support a few vibrational levels below the second dissociation limit, respectively v = 0-3 and v = 0-1, and are also included in the presented study. The complete set of resulting level energies is the most comprehensive and accurate data set for D2. The observations are compared with previous studies, both experimental and theoretical.

physics.atom-ph↗

arXiv2012

Sensitivity to a possible variation of the Proton-to-Electron Mass Ratio of Torsion-Wagging-Rotation Transitions in Methylamine (CH3NH2)

We determine the sensitivity to a possible variation of the proton-to-electron mass ratio μfor torsion-wagging-rotation transitions in the ground state of methylamine (CH3NH2). Our calculation uses an effective Hamiltonian based on a high-barrier tunneling formalism combined with extended-group ideas. The μ-dependence of the molecular parameters that are used in this model are derived and the most important ones of these are validated using the spectroscopic data of different isotopologues of methylamine. We find a significant enhancement of the sensitivity coefficients due to energy cancellations between internal rotational, overall rotational and inversion energy splittings. The sensitivity coefficients of the different transitions range from -19 to +24. The sensitivity coefficients of the 78.135, 79.008, and 89.956 GHz transitions that were recently observed in the disk of a z = 0.89 spiral galaxy located in front of the quasar PKS 1830-211 [S. Muller et al. Astron. Astrophys. 535, A103 (2011)] were calculated to be -0.87 for the first two and -1.4 for the third transition, respectively. From these transitions a preliminary upper limit for a variation of the proton to electron mass ratio of Δμ/μ< 9 x 10^{-6} is deduced.

physics.chem-ph↗

arXiv2011

Constraint on a variation of the proton-to-electron mass ratio from H2 absorption towards quasar Q2348-011

Molecular hydrogen (H2) absorption features observed in the line-of-sight to Q2348-011 at redshift zabs = 2.426 are analysed for the purpose of detecting a possible variation of the proton-to-electron mass ratio mu=mp/me. By its structure Q2348-011 is the most complex analysed H2 absorption system at high redshift so far, featuring at least seven distinctly visible molecular velocity components. The multiple velocity components associated with each transition of H2 were modeled simultaneously by means of a comprehensive fitting method. The fiducial model resulted in dmu/mu = (-0.68 +/- 2.78) x 10^-5, showing no sign that mu in this particular absorber is different from its current laboratory value. Although not as tight a constraint as other absorbers have recently provided, this result is consistent with the results from all previously analysed H2-bearing sight-lines. Combining all such measurements yields a constraint of dmu/mu < 10^-5 for the redshift range z = (2--3).

astro-ph.CO↗

arXiv2011

UV frequency metrology on CO (a3Pi); isotope effects and sensitivity to a variation of the proton-to-electron mass ratio

UV frequency metrology has been performed on the a3Pi - X1Sigma+ (0,0) band of various isotopologues of CO using a frequency-quadrupled injection-seeded narrow-band pulsed Titanium:Sapphire laser referenced to a frequency comb laser. The band origin is determined with an accuracy of 5 MHz (delta ν/ ν= 3 * 10^-9), while the energy differences between rotational levels in the a3Pi state are determined with an accuracy of 500 kHz. From these measurements, in combination with previously published radiofrequency and microwave data, a new set of molecular constants is obtained that describes the level structure of the a3Pi state of 12C16O and 13C16O with improved accuracy. Transitions in the different isotopologues are well reproduced by scaling the molecular constants of 12C16O via the common mass-scaling rules. Only the value of the band origin could not be scaled, indicative of a breakdown of the Born-Oppenheimer approximation. Our analysis confirms the extreme sensitivity of two-photon microwave transitions between nearly-degenerate rotational levels of different Omega-manifolds for probing a possible variation of the proton-to-electron mass ratio, μ=m_p/m_e, on a laboratory time scale.

physics.chem-ph↗

arXiv2011

Sensitivity of Transitions in Internal Rotor Molecules to a Possible Variation of the Proton-to-Electron Mass Ratio

Recently, methanol was identified as a sensitive target system to probe variations of the proton-to-electron mass ratio $μ$ [Jansen \emph{et al.} Phys. Rev. Lett. \textbf{106}, 100801 (2011)]. The high sensitivity of methanol originates from the interplay between overall rotation and hindered internal rotation of the molecule -- i.e. transitions that convert internal rotation energy into overall rotation energy, or vice versa, give rise to an enhancement of the sensitivity coefficient, $K_μ$. As internal rotation is a common phenomenon in polyatomic molecules, it is likely that other molecules display similar or even larger effects. In this paper we generalize the concepts that form the foundation of the high sensitivity in methanol and use this to construct an approximate model which allows to estimate the sensitivities of transitions in internal rotor molecules with $C_{3v}$ symmetry, without performing a full calculation of energy levels. We find that a reliable estimate of transition sensitivities can be obtained from the three rotational constants ($A$, $B$, and $C$) and three torsional constants ($F$, $V_3$ and $ρ$). This model is verified by comparing obtained sensitivities for methanol, acetaldehyde, acetamide, methyl formate and acetic acid with a full analysis of the molecular Hamiltonian. From the molecules considered, methanol appears to be the most suitable candidate for laboratory and cosmological tests searching for a possible variation of $μ$.

physics.chem-ph↗