Fundamental Rotational Transitions Research Articles

From Light Pipes to Substrate-Integrated Hollow Waveguides for Gas Sensing: A Review.

Absorption-based spectroscopy in the mid-infrared (MIR) spectral range (i.e., 2.5-25 μm) is an excellent choice for directly sensing trace gas analytes providing discriminatory molecular information due to inherently specific fundamental vibrational, rovibrational, and rotational transitions. Complimentarily, the miniaturization of optical components has aided the utility of optical sensing techniques in a wide variety of application scenarios that demand compact, portable, easy-to-use, and robust analytical platforms yet providing suitable accuracy, sensitivity, and selectivity. While MIR sensing technologies have clearly benefitted from the development of advanced on-chip light sources such as quantum cascade and interband cascade lasers and equally small MIR detectors, less attention has been paid to the development of modular/tailored waveguide technologies reproducibly and reliably interfacing photons with sample molecules in a compact format. In this context, the first generation of a new type of hollow waveguides gas cells-the so-called substrate-integrated hollow waveguides (iHWG)-with unprecedented compact dimensions published by the research team of Mizaikoff and collaborators has led to a paradigm change in optical transducer technology for gas sensors. Features of iHWGs included an adaptable (i.e., designable) well-defined optical path length via the integration of meandered hollow waveguide structures at virtually any desired dimension and geometry into an otherwise planar substrate, a high degree of robustness, compactness, and cost-effectiveness in fabrication. Moreover, only a few hundred microliters of gas samples are required for analysis, resulting in short sample transient times facilitating a real-time monitoring of gaseous species in virtually any concentration range. In this review, we give an overview of recent advancements and achievements since their introduction eight years ago, focusing on the development of iHWG-based mid-infrared sensor technologies. Highlighted applications ranging from clinical diagnostics to environmental and industrial monitoring scenarios will be contrasted by future trends, challenges, and opportunities for the development of next-generation portable optical gas-sensing platforms that take advantage of a modular and tailorable device design.

No evidence of phosphine in the atmosphere of Venus from independent analyses

The detection of phosphine (PH3) in the atmosphere of Venus has been recently reported based on millimeter-wave radio observations (Greaves et al. 2020), and its re-analyses (Greaves et al. 2021a/b). In this Matters Arising we perform an independent reanalysis, identifying several issues in the interpretation of the spectroscopic data. As a result, we determine sensitive upper-limits for PH3 in Venus' atmosphere (>75 km, above the cloud decks) that are discrepant with the findings in G2020 and G2021a/b. The measurements target the fundamental first rotational transition of PH3 (J=1-0) at 266.944513 GHz, which was observed with the James Clerk Maxwell Telescope (JCMT) in June 2017 and with the Atacama Large Millimeter/submillimeter Array (ALMA) in March 2019. This line's center is near the SO2 (J=309,21-318,24) transition at 266.943329 GHz (only 1.3 km/s away from the PH3 line) which represents a potential source of contamination. The JCMT and ALMA data, as presented in G2020, are at spectral resolutions comparable to the frequency separation of the two lines. Moreover, the spectral features identified are several km/s in width, and therefore do not permit distinct spectroscopic separation of the candidate spectral lines of PH3 and SO2. We present the radiative transfer modelling we have performed and then discuss the ALMA and JCMT analyses in turn.

Phase-Sensitive Vector Terahertz Electrometry from Precision Spectroscopy of Molecular Ions

This article proposes a new method for sensing THz waves that can allow electric field measurements traceable to the International System of Units and to the fundamental physical constants by using the comparison between precision measurements with cold trapped HD+ ions and accurate predictions of molecular ion theory. The approach exploits the lightshifts induced on the two-photon rovibrational transition at 55.9 THz by a THz wave around 1.3 THz, which is off-resonantly coupled to the HD+ fundamental rotational transition. First, the direction and the magnitude of the static magnetic field applied to the ion trap is calibrated using Zeeman spectroscopy of HD+. Then, a set of lightshifts are converted into the amplitudes and the phases of the THz electric field components in an orthogonal laboratory frame by exploiting the sensitivity of the lightshifts to the intensity, the polarization and the detuning of the THz wave to the HD+ energy levels. The THz electric field measurement uncertainties are estimated for quantum projection noise-limited molecular ion frequency measurements with the current accuracy of molecular ion theory. The method has the potential to improve the sensitivity and accuracy of electric field metrology and may be extended to THz magnetic fields and to optical fields.

Deuterium fractionation of nitrogen hydrides: detections of NHD and ND2

ABSTRACT Although ammonia is an abundant molecule commonly observed towards the dense interstellar medium, it has not yet been established whether its main formation route is from gas-phase ion–molecule reactions or grain-surface hydrogen additions on adsorbed nitrogen atoms. Deuterium fractionation can be used as a tool to constrain formation mechanisms. High abundances of deuterated molecules are routinely observed in the dense interstellar medium, with the ratio between deuterated molecules and the main isotopologue enhanced by several orders of magnitude with respect to the elemental D/H ratio. In the case of ammonia, the detection of its triply deuterated isotopologue hints at high abundances of the deuterated intermediate nitrogen radicals, ND, NHD, and ND2. So far however, only ND has been detected in the interstellar medium. In this paper, to constrain the formation of ammonia, we aim at determining the NHD/NH2 and ND2/NHD abundance ratios, and compare them with the predictions of both pure gas-phase and grain-surface chemical models. We searched for the fundamental rotational transitions of NHD and ND2 towards the class 0 protostar IRAS16293−2422, towards which NH, NH2 and ND had been previously detected. Both NHD and ND2 are detected in absorption towards the source. The relative abundance ratios NH2:NHD:ND2 are close to 8:4:1. These ratios can be reproduced by our gas-phase chemical model within a factor of 2–3. Statistical ratios as expected from grain-surface chemistry are also consistent with our data. Further investigations of the ortho-to-para ratio in ND2 , both theoretical and observational, could bring new constraints to better understand nitrogen hydride chemistry.

Precise test of quantum electrodynamics and determination of fundamental constants with HD+ ions.

Bound three-body quantum systems are important for fundamental physics1,2 because they enable tests of quantum electrodynamics theory and provide access to the fundamental constants of atomic physics and to nuclear properties. Molecular hydrogen ions, the simplest molecules, are representative of this class3. The metastability of the vibration-rotation levels in their ground electronic states offers the potential for extremely high spectroscopic resolution. Consequently, these systems provide independent access to the Rydberg constant (R∞), the ratios of the electron mass to the proton mass (me/mp) and of the electron mass to the deuteron mass (me/md), the proton and deuteron nuclear radii, and high-level tests of quantum electrodynamics4. Conventional spectroscopy techniques for molecular ions5-14 have long been unable to provide precision competitive with that of ab initio theory, which has greatly improved in recent years15. Here we improve our rotational spectroscopy technique for a sympathetically cooled cluster of molecular ions stored in a linear radiofrequency trap16 by nearly two orders in accuracy. We measured a set of hyperfine components of the fundamental rotational transition. An evaluation resulted in the most accurate test of a quantum-three-body prediction so far, at the level of 5×10-11, limited by the current uncertainties of the fundamental constants. We determined the value of the fundamental constants combinations [Formula: see text] and mp/me with a fractional uncertainty of 2×10-11, in agreement with, but more precise than, current Committee on Data for Science and Technology values. These results also provide strong evidence of the correctness of previous key high-precision measurements and a more than 20-fold stronger bound for a hypothetical fifth force between a proton and a deuteron.

Modelling of Rib channel waveguides based on silicon-on-sapphire at 4.67 μm wavelength for evanescent field gas absorption sensor

The mid-IR spectrum contains absorption peaks for a wide variety of trace gases, for instance, N2O, CO, CO2, H2O, NO2, NH3, NO and CH4 etc. These gases strongly absorb in the mid-IR >2.5 μm spectral region due to their fundamental rotational and vibrational transitions. In this work, we propose a silicon-on-sapphire (SOS) rib waveguide design at 4.67 μm for carbon monoxide (CO) gas sensing based on the evanescent field absorption. The exponentially decaying evanescent fields in the lower index region of a waveguide offer a high perspective in the realization of a variety of sensors. Numerous waveguide dimensions are modelled and studied in order to achieve an optimal evanescent field ratio (EFR) with lowest possible total losses of the waveguides. The total losses of these waveguides are in the range of 2.59–3.89 dB and 1.51–1.76 dB for TE and TM modes, respectively.

Silicon on silicon dioxide slot waveguide evanescent field gas absorption sensor

Several trace gases such as H2O, CO, CO2, NO, N2O, NO2 and CH4 strongly absorb in the mid-IR spectral region due to their fundamental rotational and vibrational transitions. In this work, we propose an evanescent field absorption gas sensor based on silicon/silicon dioxide slot waveguide at 3.39 μm for sensing of methane gas. These waveguides can provide the highest evanescent field ratio (EFR) > 47% with adequate dimensions. Higher EFR values often come at an expense of higher propagation losses. These waveguides have relatively higher losses as compared to conventional waveguides, such as rib and slab waveguides, as these fundamental losses are static and the proposed sensing mechanism is established on the incremental loss due to the absorption of the gas. Therefore, incident power can always be incremented to compensate the waveguide losses.

An evanescent field absorption gas sensor at mid-IR 3.39 μm wavelength

Trace gases such as H2O, CO, CO2, NO, N2O, NO2 and CH4 strongly absorb in the mid-IR (>2.5 μm) spectral region due to their fundamental rotational and vibrational transitions. CH4 gas is relatively non-toxic, however, it is extremely explosive when mixed with other chemicals in levels as low as 5% and it can cause death by asphyxiation. In this work, we propose a silicon strip waveguide at 3.39 μm for CH4 gas sensing based on the evanescent field absorption. These waveguides can provide the highest evanescent field ratio (EFR)>55% with adequate dimensions. Moreover, EFR and sensitivity of the sensor are highly dependent on the length of the waveguide up to a certain limit. Therefore, it is always a compromise between the length of the waveguide and EFR in order to obtain greater sensitivity.

Stratified NH and ND emission in the prestellar core 16293E in L1689N

High degrees of deuterium fractionation are commonly found in cold prestellar cores and in the envelopes around young protostars. As it brings strong constraints to chemical models, deuterium chemistry is often used to infer core history or molecule formation pathways. Whereas a large number of observations is available regarding interstellar deuterated stable molecules, relatively little is known about the deuteration of hydride radicals, as their fundamental rotational transitions are at high frequencies where the atmosphere is mostly opaque. Nitrogen hydride radicals are important species in nitrogen chemistry, as they are thought to be related to ammonia formation. Observations have shown that ammonia is strongly deuterated, with [NH2D]/[NH3] ~ 10%. Models predict similarly high [ND]/[NH] ratios, but so far only one observational determination of this ratio is available, towards the envelope of the protostar IRAS16293-2422. In order to test model predictions, we aim here at determining [ND]/[NH] in a dense, starless core. We observed NH and ND in 16293E with the HIFI spectrometer on board the Herschel Space Observatory as part of the CHESS guaranteed time key programme, and derived the abundances of these two species using a non-LTE non-local radiative transfer model. Both NH and ND are detected in the source, with ND in emission and NH in absorption against the continuum arising from the cold dust emission. Our model shows however that the ND emission and the NH absorption originate from different layers in the cloud, as further evidenced by their different velocities. In the central region of the core, we can set a lower limit to the [ND]/[NH] ratio of ~2%. This estimate is consistent with recent pure gas-phase models of nitrogen chemistry

High-resolution rotational spectroscopy of iminosilylene, HNSi

By means of Fourier transform microwave spectroscopy of a supersonic beam, the fundamental rotational transition of isotopic and vibrationally excited iminosilylene, HNSi, has been detected. In addition to seven isotopic species, vibrational satellite transitions from more than 30 vibrationally excited states, including the three fundamental modes, have been detected. Those from ν2 are particularly intense, enabling detection of transitions from as high as (0,220,0) (i.e. ∼10,000 cm−1 above ground). At high spectral resolution, well-resolved nitrogen quadrupole structure has been observed in nearly every transition. Excitation of ν1 or ν3 changes eQq(N) little, but eQq(N) systematically decreases with increasing excitation of the ν2 bend, from a value of 0.376(5) MHz for (0,00,0) to −2.257(5) MHz for (0,200,0). With the large amount of new data in hand, it has also been possible to determine the leading vibration–rotation constants (αi and γi) for ν2 or ν3 to high precision, and derive a revised semi-empirical equilibrium structure for this fundamental triatomic molecule. Various electronic and molecular properties of iminosilylene have been calculated at the coupled cluster level of theory, and these generally agree well with experiment and previous calculations. An unsuccessful search for HSiN, a highly polar isomer calculated to lie nearly 3 eV above HNSi, is also reported.

Two-photon rotational action spectroscopy of cold OH- at 1 ppb accuracy.

The fundamental rotational transition J = 1←0 of the anion OH(-) has been measured by cooling mass-selected OH(-) ions to 10 K in a 22-pole ion trap and applying a novel rotational-rovibrational two-photon scheme. A transition frequency of (1 123 101.0410 ± 0.0014) MHz was obtained with so far unprecedented accuracy. The general application of the presented action-spectroscopy scheme to other anions and cations is discussed.

The CN/C15N isotopic ratio towards dark clouds

Understanding the origin of the composition of solar system cosmomaterials is a central question, not only in the cosmochemistry and astrochemistry fields, and requires various approaches to be combined. Measurements of isotopic ratios in cometary materials provide strong constraints on the content of the protosolar nebula. Their relation with the composition of the parental dark clouds is, however, still very elusive. In this paper, we bring new constraints based on the isotopic composition of nitrogen in dark clouds, with the aim of understanding the chemical processes that are responsible for the observed isotopic ratios. We have observed and detected the fundamental rotational transition of C$^{15}$N towards two starless dark clouds, L1544 and L1498. We were able to derive the column density ratio of C$^{15}$N over $^{13}$CN towards the same clouds, and obtain the CN/C$^{15}$N isotopic ratios, which were found to be $500\pm75$ for both L1544 and L1498. These values are therefore marginally consistent with the protosolar value of 441. Moreover, this ratio is larger than the isotopic ratio of nitrogen measured in HCN. In addition, we present model calculations of the chemical fractionation of nitrogen in dark clouds, which make it possible to understand how CN can be deprived of $^{15}$N and HCN can simultaneously be enriched in heavy nitrogen. The non-fractionation of N2H+, however, remains an open issue and we propose some chemical way of alleviating the discrepancy between model predictions and the observed ratios.

Ortho-to-Para Ratio in Interstellar Water on the Sightline toward Sagittarius B2(N)

The determination of the water ortho-to-para ratio (OPR) is of great interest for studies of the formation and thermal history of water ices in the interstellar medium and protoplanetary disk environments. We present new Herschel observations of the fundamental rotational transitions of ortho- and para-water on the sightline toward Sagittarius B2(N), which allow improved estimates of the measurement uncertainties due to instrumental effects and assumptions about the excitation of water molecules. These new measurements, suggesting a spin temperature of 24-32 K, confirm the earlier findings of an OPR below the high-temperature value on the nearby sightline toward Sagittarius B2(M). The exact implications of the low OPR in the galactic center molecular gas remain unclear and will greatly benefit from future laboratory measurements involving water freeze-out and evaporation processes under low-temperature conditions, similar to those present in the galactic interstellar medium. Given the specific conditions in the central region of the Milky Way, akin to those encountered in active Galactic nuclei, gas-phase processes under the influence of strong X-ray and cosmic ray ionization also have to be carefully considered. We summarize some of the latest laboratory measurements and their implications here.

Detection of Nitrogen-Protonated Nitrous Oxide (HNNO+) by Rotational Spectroscopy

The rotational spectrum of nitrogen-protonated nitrous oxide (HNNO(+)), an isomer whose existence was first inferred from kinetic studies more than 30 years ago, has now been detected by Fourier transform microwave spectroscopy, guided by new high-level coupled-cluster calculations of its molecular structure. From high-resolution measurements of the hyperfine splitting in its fundamental rotational transition, the rotational constant (B + C)/2 and the quadrupole tensor element χaa(N) for both nitrogen atoms have been precisely determined. The derived constants agree well with quantum-chemical calculations here and others in the literature. The χaa(N) values for the two isomers of protonated nitrous oxide are qualitatively consistent with the valence bond description of H-N═N(+)═O for the electronic structure of the nitrogen-protonated form and N≡N(+)-O-H for the oxygen-protonated form. HNNO(+) is found to be 2-4 times less abundant than NNOH(+) under a range of experimental conditions, as might be expected because this metastable isomer is known to be only ∼6 kcal mol(-1) less stable than ground-state NNOH(+) from kinetic measurements by Ferguson and co-workers.

The 15N-enrichment in dark clouds and Solar System objects

The line intensities of the fundamental rotational transitions of H13CN and HC15N were observed towards two prestellar cores, L183 and L1544, and lead to molecular isotopic ratios 140⩽14N/15N⩽250 and 140⩽14N/15N⩽360, respectively. The range of values reflect genuine spatial variations within the cores. A comprehensive analysis of the available measurements of the nitrogen isotopic ratio in prestellar cores show that molecules carrying the nitrile functional group appear to be systematically 15N-enriched compared to those carrying the amine functional group. A chemical origin for the differential 15N-enhancement between nitrile- and amine-bearing interstellar molecules is proposed. This sheds new light on several observations of Solar System objects: (i) the similar N isotopic fractionation in Jupiter’s NH3 and solar wind N+; (ii) the 15N-enrichments in cometary HCN and CN (that might represent a direct interstellar inheritance); and (iii) 15N-enrichments observed in organics in primitive cosmomaterials. The large variations in the isotopic composition of N-bearing molecules in Solar System objects might then simply reflect the different interstellar N reservoirs from which they are originating.

An old disk still capable of forming a planetary system

From the masses of the planets orbiting the Sun, and the abundance of elements relative to hydrogen, it is estimated that when the Solar System formed, the circumstellar disk must have had a minimum mass of around 0.01 solar masses within about 100 astronomical units of the star. (One astronomical unit is the Earth-Sun distance.) The main constituent of the disk, gaseous molecular hydrogen, does not efficiently emit radiation from the disk mass reservoir, and so the most common measure of the disk mass is dust thermal emission and lines of gaseous carbon monoxide. Carbon monoxide emission generally indicates properties of the disk surface, and the conversion from dust emission to gas mass requires knowledge of the grain properties and the gas-to-dust mass ratio, which probably differ from their interstellar values. As a result, mass estimates vary by orders of magnitude, as exemplified by the relatively old (3-10 million years) star TW Hydrae, for which the range is 0.0005-0.06 solar masses. Here we report the detection of the fundamental rotational transition of hydrogen deuteride from the direction of TW Hydrae. Hydrogen deuteride is a good tracer of disk gas because it follows the distribution of molecular hydrogen and its emission is sensitive to the total mass. The detection of hydrogen deuteride, combined with existing observations and detailed models, implies a disk mass of more than 0.05 solar masses, which is enough to form a planetary system like our own.

Hot, metastable hydronium ion in the Galactic centre: formation pumping in X-ray-irradiated gas?

With a 3.5 m diameter telescope passively cooled to approximately 80 K, and a science payload comprising two direct detection cameras/medium resolution imaging spectrometers (PACS and SPIRE) and a very high spectral resolution heterodyne spectrometer (HIFI), the Herschel Space Observatory is providing extraordinary observational opportunities in the 55-670 μm spectral range. HIFI has opened for the first time to high-resolution spectroscopy the submillimetre band that includes the fundamental rotational transitions of interstellar hydrides, the basic building blocks of astrochemistry. We discuss a recent HIFI discovery of metastable rotational transitions of the hydronium ion (protonated water, H(3)O(+)), with rotational level energies up to 1200 K above the ground state, in absorption towards Sagittarius B2(N) in the Galactic centre. Hydronium is an important molecular ion in the oxygen chemical network. Earlier HIFI observations have indicated a general deficiency of H(3)O(+) in the diffuse gas in the Galactic disc. The presence of hot H(3)O(+) towards Sagittarius B2(N) thus appears to be related to the unique physical conditions in the central molecular zone, manifested, for example, by the widespread presence of abundant H(3)(+). One intriguing theory for the high rotational temperature characterizing the population of the H(3)O(+) metastable levels may be formation pumping in molecular gas irradiated by X-rays emitted by the Galactic centre black hole. Alternatively, the pervasive presence of enhanced turbulence in the central molecular zone may give rise to shocks in the lower-density medium that is exposed to energetic radiation.

SUBMILLIMETER LINE SPECTRUM OF THE SEYFERT GALAXY NGC 1068 FROM THEHERSCHEL-SPIRE FOURIER TRANSFORM SPECTROMETER

The first complete submillimetre spectrum (190-670um) of the Seyfert 2 galaxy NGC1068 has been observed with the SPIRE Fourier Transform Spectrometer onboard the {\it Herschel} Space Observatory. The sequence of CO lines (Jup=4-13), lines from water, the fundamental rotational transition of HF, two o-H_2O+ lines and one line each from CH+ and OH+ have been detected, together with the two [CI] lines and the [NII]205um line. The observations in both single pointing mode with sparse image sampling and in mapping mode with full image sampling allow us to disentangle two molecular emission components, one due to the compact circum-nuclear disk (CND) and one from the extended region encompassing the star forming ring (SF-ring). Radiative transfer models show that the two CO components are characterized by density of n(H_2)=10^4.5 and 10^2.9 cm^-3 and temperature of T=100K and 127K, respectively. The comparison of the CO line intensities with photodissociation region (PDR) and X-ray dominated region (XDR) models, together with other observational constraints, such as the observed CO surface brightness and the radiation field, indicate that the best explanation for the CO excitation of the CND is an XDR with density of n(H_2) 10^4 cm^-3 and X-ray flux of 9 erg s^-1 cm^-2, consistent with illumination by the active galactic nucleus, while the CO lines in the SF-ring are better modeled by a PDR. The detected water transitions, together with those observed with the \her \sim PACS Spectrometer, can be modeled by an LVG model with low temperature (T_kin \sim 40K) and high density (n(H_2) in the range 10^6.7-10^7.9 cm^-3).

Observation of a rotational transition of trapped and sympathetically cooled molecular ions

We demonstrate rotational excitation of molecular ions that are sympathetically cooled by laser-cooled atomic ions to a temperature as low as ca. 10 mK. The molecular hydrogen ions HD+ and the fundamental rotational transition $(v=0,\, N=0)\rightarrow(v'=0,\, N'=1)$ at 1.3 THz, the most fundamental dipole-allowed rotational transition of any molecule, are used as a test case. This transition is here observed for the first time directly. Rotational laser cooling was employed in order to increase the signal, and resonance-enhanced multiphoton dissociation was used as detection method. The black-body-radiation-induced rotational excitation is also observed. The extension of the method to other molecular species is briefly discussed.

Herschel/HIFI measurements of the ortho/para ratio in water towards Sagittarius B2(M) and W31C

We present Herschel/HIFI observations of the fundamental rotational transitions of ortho- and para-H$_2^{16}$O and H$_2^{18}$O in absorption towards Sagittarius~B2(M) and W31C. The ortho/para ratio in water in the foreground clouds on the line of sight towards these bright continuum sources is generally consistent with the statistical high-temperature ratio of 3, within the observational uncertainties. However, somewhat unexpectedly, we derive a low ortho/para ratio of $2.35 \pm 0.35$, corresponding to a spin temperature of $\sim$27~K, towards Sagittarius~B2(M) at velocities of the expanding molecular ring. Water molecules in this region appear to have formed with, or relaxed to, an ortho/para ratio close to the value corresponding to the local temperature of the gas and dust.