Rotational Line Intensities Research Articles

Self-generated ultraviolet radiation in molecular shock waves

Context. The energetics and physical conditions of the interstellar medium and feedback processes remain challenging to probe. Aims. Shocks, modelled over a broad range of parameters, are used to construct a new tool to deduce the mechanical energy and physical conditions from observed atomic or molecular emission lines. Methods. We compute magnetised, molecular shock models with velocities Vs = 5–80 km s−1, pre-shock proton densities nH = 102–106 cm−3, weak or moderate magnetic field strengths, and in the absence or presence of an external UV radiation field. These parameters represent the broadest published range of physical conditions for molecular shocks. As a key shock tracer, we focus on the production of CH+ and post-process the radiative transfer of its rovibrational lines. We develop a simple emission model of an ensemble of shocks for connecting any observed emission lines to the mechanical energy and physical conditions of the system. Results. For this range of parameters, we find the full diversity (C-, C*-, CJ-, and J-type) of magnetohydrodynamic shocks. H2 and H are dominant coolants, with up to 30% of the shock kinetic flux escaping in Lyα photons. The reformation of molecules in the cooling tail means H2 is even a good tracer of dissociative shocks and shocks that were initially fully atomic. The known shock tracer CH+ can also be a significant coolant, reprocessing up to 1% of the kinetic flux. Its production and excitation is intimately linked to the presence of H2 and C+. For each shock model we provide integrated intensities of rovibrational lines of H2, CO, and CH+, and atomic H lines, and atomic fine-structure and metastable lines. We demonstrate how to use these shock models to deduce the mechanical energy and physical conditions of extragalactic environments. As a template example, we interpret the CH+(1−0) emission from the Eyelash starburst galaxy. A mechanical energy injection rate of at least 1011 L⊙ into molecular shocks is required to reproduce the observed line. We find that shocks with velocities as low as 5 km s−1 irradiated by a strong UV field are compatible with the available energy budget. The low-velocity, externally irradiated shocks are at least an order magnitude more efficient than the most efficient shocks with no external irradiation in terms of the total mechanical energy required. We predict differences of more than two orders of magnitude in the intensities of the pure rotational lines of CO, Lyα, and the metastable lines of O, S+, and N between representative models of low-velocity (Vs ~ 10 km s−1) externally irradiated shocks and higher-velocity shocks (Vs ≥ 50 km s−1) with no external irradiation. Conclusions. Shock modelling over an extensive range of physical conditions allows for the interpretation of challenging observations of broad line emission from distant galaxies. Our new method opens up a promising avenue to quantitatively probe the physical conditions and mechanical energy of galaxy-scale gas flows.

Complete rotational assignment of the (0,0) vibrational band of the A1Π–X1Σ+ transition of carbon monosulfide

Carbon monosulfide (CS) generated in the S(1D) + CS2 → CS(X1Σ+) + S2 reaction was detected with the laser-induced fluorescence via the A1Π–X1Σ+ transition. The rotational structure of the (0,0) vibrational band is considerably deformed by the perturbation between the vibrational levels v = 0 of A1Π and v = 10 of a'3Σ+ states. Both the appearance wavelengths and peak intensities of many rotational lines are varied by the size of the perturbation. The precise assignment of the rotational lines of the spin-forbidden transition a'3Σ+−X1Σ+ (10,0) bands has been given. The observed spectrum was well-reproduced with higher accuracy than any previous analysis.

OH mid-infrared emission as a diagnostic of H2O UV photodissociation

Context. Water is an important molecule in interstellar and circumstellar environments. Previous observations of mid-infrared (IR) rotational lines of OH toward star-forming regions suggest that OH emission may be used to probe the photodissociation of water. Aims. Our goal is to propose a method to quantify H2O photodissociation and measure the local ultraviolet (UV) flux from observations of mid-IR OH lines. Methods. Cross sections for the photodissociation of H2O resolving individual electronic, vibrational, and rotational states of the OH fragment are collected. The state distribution of nascent OH following H2O photodissociation is computed for various astrophysically relevant UV radiation fields (e.g., a single Lyα line or a broadband spectrum). These distributions are incorporated in a new molecular excitation code called GROSBETA, which includes radiative pumping, collisional (de)excitation, and prompt emission (i.e., following the production of OH in excited states). The influence of the photodissociation rate of H2O, the spectral shape of the UV radiation field, the density, the temperature of the gas, and the strength of the IR background radiation field on the integrated line intensities are studied in detail. As a test case, our model is compared to Spitzer-IRS observations at the tip of the HH 211 bow-shock. Results. The OH rotational line intensities in the range 9–16 μm, covering rotational transitions with Nup = 18–45, are proportional to the column density of H2O photodissociated per second by photons in the range 114–143 nm (denoted as ΦB̃) and do not depend on other local properties such as the IR radiation field, the density, or the kinetic temperature. Provided an independent measurement of the column density of water is available, the strength of the local UV radiation field can be deduced with good accuracy, regardless of the exact shape of the UV field. In contrast, OH lines at longer far-IR wavelengths are primarily produced by IR radiative pumping and collisions, depending on the chemical pumping rate defined as 𝒟B̃ = ΦB̃/N(OH) and on the local physical conditions (nH, TK, IR radiation field). Our model successfully reproduces the OH mid-IR lines in the 10–16 μm range observed toward the tip of the HH 211 bow-shock and shows that the jet shock irradiates its surroundings, exposing H2O to a UV photon flux that is about 5 × 103 times larger than the standard interstellar radiation field. We also find that chemical pumping by the reaction H2 + O may supplement the excitation of lines in the range 16–30 μm, suggesting that these lines could also be used to measure the two-body formation rates of OH. Conclusions. The mid-IR lines of OH constitute a powerful diagnostic for inferring the photodissociation rate of water and thus the UV field that water is exposed to. Future JWST-MIRI observations will be able to map the photodestruction rate of H2O in various dense (nH ≳ 106 cm−3) and irradiated environments and provide robust estimates of the local UV radiation field.

Infrared spectroscopy of an endohedral water in fullerene.

An infrared absorption spectroscopy study of the endohedral water molecule in a solid mixture of H2O@C60 and C60 was carried out at liquid helium temperature. From the evolution of the spectra during the ortho-para conversion process, the spectral lines were identified as para-H2O and ortho-H2O transitions. Eight vibrational transitions with rotational side peaks were observed in the mid-infrared: ω1, ω2, ω3, 2ω1, 2ω2, ω1 + ω3, ω2 + ω3, and 2ω2 + ω3. The vibrational frequencies ω2 and 2ω2 are lower by 1.6% and the rest by 2.4%, as compared to those of free H2O. A model consisting of a rovibrational Hamiltonian with the dipole and quadrupole moments of H2O interacting with the crystal field was used to fit the infrared absorption spectra. The electric quadrupole interaction with the crystal field lifts the degeneracy of the rotational levels. The finite amplitudes of the pure v1 and v2 vibrational transitions are consistent with the interaction of the water molecule dipole moment with a lattice-induced electric field. The permanent dipole moment of encapsulated H2O is found to be 0.50 ± 0.05 D as determined from the far-infrared rotational line intensities. The translational mode of the quantized center-of-mass motion of H2O in the molecular cage of C60 was observed at 110 cm-1 (13.6 meV).

The CO universe: modelling CO emission and H2 abundance in cosmological galaxy formation simulations

ABSTRACT We devise a physical model of formation and distribution of molecular gas clouds (MGCs) in galaxies. We use the model to predict the intensities of rotational transition lines of carbon monoxide (CO) and the molecular hydrogen (H2) abundance. Using the outputs of IllustrisTNG cosmological simulations, we populate MGCs of unresolved sizes in individual simulated galaxies, where the effect of the interstellar radiation field with dust attenuation is also taken into account. We then use the publicly available code despotic (Derive the Energetics and SPectra of Optically Thick Interstellar Clouds) to compute the CO line luminosities and H2 densities without assuming the CO-to-H2 conversion factor (αCO). Our method allows us to study the spatial and kinematic structures traced by CO(1–0) and higher transition lines. We compare the CO luminosities and H2 masses with recent observations of galaxies at low and high redshifts. Our model reproduces well the observed CO–luminosity function and the estimated H2 mass in the local UniverseAbout 10 per cent of molecules in the Universe reside in dwarf galaxies with stellar masses lower than 109 M⊙, but the galaxies are generally ‘CO-dark’ and have typically high αCO. Our model predicts generally lower CO line luminosities than observations at redshifts z ≳ 1–2. We argue that the difference can be explained by the highly turbulent structure suggested for the high-redshift star-forming galaxies.

Measurement of rotational temperature of AlO molecule from Fourier transform spectrum of the 0–0 band of B2Σ+–X2Σ+ band system

The astrophysical importance of AlO molecule and its astronomical significance is well known. The existence of AlO molecule in the atmospheres of M type of stars is reported. The identification of B–X system in spectrum of some normal Mira giants and Mira variables is reported in literature. In the present work, the high resolution spectrum of the B2 Σ+ –X2 Σ+ system of AlO was recorded on a Fourier Transform Spectrometer. By measuring the intensities of the well-resolved rotational lines of R1 and R2 branches of the (0–0) band measured the rotational temperature is calculated which is 1967 ± 75 K.

FIR Spectroscopy of the Galactic Center: Hot and Warm Molecular Gas

AbstractThe angular resolution (~10″) achieved by the Herschel Space Observatory ~3.5 m telescope at FIR wavelengths allowed us to roughly separate the emission toward the inner parsec of the galaxy (the central cavity) from that of the surrounding circumnuclear disk (the CND). The FIR spectrum toward Sgr A* is dominated by intense [O iii], [O i], [C ii], [N iii], [N ii], and [C i] fine-structure lines (in decreasing order of luminosity) arising in gas irradiated by the strong UV field from the central stellar cluster. The high-J CO rotational line intensities observed at the interface between the inner CND and the central cavity are consistent with a hot isothermal component at Tk ≈ 103.1 K and n(H2)≈ 104 cm−3. They are also consistent with a distribution of lower temperatures at higher gas density, with most CO at Tk≈300 K. The hot CO component (either the bulk of the CO column density or just a small fraction depending on the above scenario) likely results from a combination of UV and shock-driven heating. If UV-irradiated and heated dense clumps do not exist, shocks likely dominate the heating of the hot molecular gas component. Although this component is beam diluted in our FIR observations, it may be resolved at much higher angular resolution. An ALMA project using different molecular tracers to characterize UV-irradiated shocks in the innermost layers of the CND is ongoing.

Methanimine in interstellar medium: line intensities

Methanimine \((\hbox {CH}_2\hbox {NH})\) in the gas phase has been of great interest for both the spectroscopists and astronomers, as it is precursor of aminoacetonitrile \((\hbox {NH}_2\hbox {CH}_2\hbox {CN})\). The aminoacetonitrile is one of the key molecules of Strecker type synthesis, which is proposed to form glycine \((\hbox {NH}_2\hbox {CH}_2\hbox {COOH})\), the simplest amino acid. A number of spectral lines of methanimine have been identified in the interstellar space. However, there may be other spectral lines which may help in its identification in the interstellar space. We have investigated the intensities of rotational lines of methanimine. The methanimine has both a and b type rotational transitions. The network of transitions is complex. In this theoretical approach, we have found that in addition to the observed lines, there are more than 100 lines which may help in identification of methanimine. The transitions between some doublets may show the MASER action.

Measurements of the number density of water molecules in plasma by using a combined spectral−probe method

A novel method for measuring the number density of water molecules in low-temperature plasma is developed. The absolute intensities of rotational lines of the (0,0) band of the OH(A2Σ–X2П) transition are used. Lines with sufficiently large rotational quantum numbers referring to the so-called “hot” group of molecules produced by electron-impact dissociative excitation of water molecules are chosen for measurements. The excitation rate of a process with a known cross section is determined by measuring the parameters of plasma electrons by means of the probe method. The measured number densities of molecules are compared with those in the initial plasma-forming mixture. The time evolution of the particle densities in plasma is investigated. The problems of the sensitivity and applicability of the absolute spectral method are considered.

Dissipation of turbulence by magnetohydrodynamic shock waves

AbstractWe characterise steady, one-dimensional fast and slow magnetohydrodynamic (MHD) shocks using a two-fluid model. Fast MHD shocks are magnetically driven, forcing ions to stream through the neutral gas ahead of the shock front. This magnetic precursor heats the gas sufficiently to create a large, warm transition zone where all fluid variables only weakly change in the shock front. In contrast, slow MHD shocks are driven by gas pressure where neutral species collide with ion species in a thin hot slab that closely resembles an ordinary gas dynamic shock.We computed observational diagnostics for fast and slow shocks at velocities vs=2–4 km/s and preshock Hydrogen nuclei densities nH = 102-4 cm−3. We followed the abundances of molecules relevant for a simple oxygen chemistry and include cooling by CO, H2 and H2O. Estimates of intensities of 12CO rotational lines show that high-J lines, above J = 6 → 5, are more strongly excited in slow MHD shocks.

A theoretical and experimental study of pressure broadening of the oxygen A-band by helium.

The rotationally resolved magnetic dipole absorption spectrum of the oxygen A-band b(1)Σ(g)(+)(v=0) <- X(3)Σ(g)(-)(v=0) perturbed by collisions with helium was studied theoretically using the impact approximation. To calculate the relaxation matrix, scattering calculations were performed on a newly computed helium-oxygen (b(1)Σ(g)(+)) interaction potential as well as on a helium-oxygen (X(3)Σ(g)(-)) interaction potential from the literature. The calculated integrated line cross sections and broadening coefficients are in good agreement with experimental results from the literature. Additionally, cavity ring-down experiments were performed in the wings of the spectral lines for a quantitative study of line-mixing, i.e., the redistribution of rotational line intensities by helium-oxygen collisions. It is shown that inclusion of line-mixing in the theory is required to reproduce the experimentally determined absolute absorption strengths as a function of the density of the helium gas.

Self and N2 collisional broadening of far-infrared methane lines measured at the SOLEIL synchrotron

Following our recent study devoted to measurements of intensities of pure rotation lines of methane, room temperature far infrared spectra of methane diluted in nitrogen at five total pressures between 100 and 800hPa have been recorded at the AILES beamline of the SOLEIL synchrotron. One hundred and five N2 broadening coefficients of methane pure rotation lines have been measured in the 83–261cm−1 spectral range using multi-spectrum non-linear least squares fitting of Voigt profiles. Pressure-induced line shifts were not needed to fit the spectra to the noise level and line mixing effects were neglected. One hundred and seventy-six self broadening coefficients have also been measured in the 59–288cm−1 spectral range using the pure methane spectra recorded in our previous work. The measured N2 broadening coefficients were compared to semi-classical calculations.

Photofragmentations, state interactions, and energetics of Rydberg and ion-pair states: Two-dimensional resonance enhanced multiphoton ionization of HBr via singlet-, triplet-, Ω = 0 and 2 states

Mass spectra were recorded for one-colour resonance enhanced multiphoton ionization (REMPI) of H(i)Br (i = 79, 81) for the two-photon resonance excitation region 79,040-80,300 cm(-1) to obtain two-dimensional REMPI data. The data were analysed in terms of rotational line positions, intensities, and line-widths. Quantitative analysis of the data relevant to near-resonance interactions between the F(1)Δ(2)(v' = 1) and V(1)Σ(+)(v' = m + 7) states gives interaction strengths, fractional state mixing, and parameters relevant to dissociation of the F state. Qualitative analysis further reveals the nature of state interactions between ion-pair states and the E(1)Σ(+) (v' = 1) and H(1)Σ(+)(v' = 0) Rydberg states in terms of relative strengths and J' dependences. Large variety in line-widths, depending on electronic states and J' quantum numbers, is indicative of number of different predissociation channels. The relationship between line-widths, line-shifts, and signal intensities reveals dissociation mechanisms involving ion-pair to Rydberg state interactions prior to direct or indirect predissociations of Rydberg states. Quantum interference effects are found to be important. Moreover, observed bromine atom (2 + 1) REMPI signals support the importance of Rydberg state predissociation channels. A band system, not previously observed in REMPI, was observed and assigned to the k(3)Π(0)(v' = 0) ←← X transition with band origin 80,038 cm(-1) and rotational parameter B(v('))=7.238 cm(-1).

NON-LTE EFFECTS ON THE H3+ROVIBRATIONAL POPULATION IN THE JOVIAN IONOSPHERE

We investigate non-LTE effects on the H₃? level populations to help the analysis of the observed 2 and 3.5 micron H₃? emissions from the Jovian ionosphere. We begin by constructing a simple three-level model, in order to compute the intensity ratio of the R(3,4) line in the hot band to the Q(1,0) line in the fundamental band, which have been observed in the Jovian auroral regions. We find that non-LTE effects produce only small changes in the intensity ratios for ambient H₂ densities less than or equal to 5×10 11 ㎝ ?3 . We then construct two comprehensive models by including all the collisional and radiative transitions between pairs of more than a thousand known H₃? rovibrational levels with energies less than 10000 ㎝ ?1 . By employing these models, we find that the intensity ratios of the lines in the hot and fundamental bands are affected greatly by non-LTE effects, but the details depend sensitively on the number of collisional and radiative transitions included in the models. Non-LTE effects on the rovibrational population become evident at about the same ambient H₂ densities in the comprehensive models as in the three-level model. However, the models show that rotational temperatures derived from the intensities of rotational lines in the v₂ and 2v₂ bands may differ significantly from the ambient temperatures in the non-LTE regime. We find that significant non-LTE effects appear near and above the H₃? peak, and that the kinetic temperatures in the Jovian thermospheric temperatures derived from the observed line ratios in the 2 and 3.5 micron H₃? emissions are highly model dependent.

Time-dependent modelling of the molecular line emission from shock waves in outflow sources

We have developed further the technique of time-dependent modelling of magnetohydrodynamic shock waves, with a view to interpreting the molecular line emission from outflow sources. The extensively observed source L1157 B1 was chosen as an exemplar of the application of this technique. The dynamical age of the shock wave model was varied in the range 500 ≤t≤ 5000 yr, with the best fit to the observed line intensities being obtained for t= 1000 yr; this is of the same order as the dynamical age derived by Gueth, Guilloteau & Bachiller from their observations of L1157 B1. The emission line spectra of H2, CO, SiO, ortho- and para-H2O, ortho- and para-NH3, and A- and E-type CH3OH were calculated in parallel with the dynamical and chemical parameters of the model, using the ‘large velocity gradient’ (LVG) approximation to the line transfer problem. We compared the predictions of the models with the observed intensities of emission lines of H2, CO, SiO, ortho-H2O, ortho-NH3 and CH3OH, which include recent Herschel satellite measurements. In the case of SiO, we show (in Appendix A) that extrapolations of the collisional rate coefficients beyond the range of kinetic temperature for which they were originally calculated lead to spurious rotational line intensities and profiles. The computed emission-line spectra of SiO, NH3 and CH3OH are shown to depend on the assumed initial composition of the grain mantles, from whence they are released, by sputtering in the shock wave, into the gas phase. The dependence of the model predictions on the adopted form of the grain-size distribution is investigated in Appendix B; the corresponding integral line intensities are given in tabular form, for a range of C-type shock speeds, in the online Supporting Information.

WhyCOBEand CN spectroscopy cosmic background radiation temperature measurements differ, and a remedy

In 2004, the cosmic background radiation (CBR) temperature Tγ(CN) determined from interstellar CN absorption spectra was found to be 50 ± 20 mK higher than the COBE bolometer measured value. It was proposed that this was due, at least in part, to an error in the evaluation of the rotational components of the oscillator strengths of the rovibronic transitions corresponding to the CN B 2Σ+–X 2Σ+(0 − 0), R(0), R(1) and P(1) lines. Corrections to the standard Hönl–London (HL) rotational line intensity factors used were determined. New data on interstellar CN absorption show that Tγ(CN) is 29 ± 2 mK greater than the latest value of the cosmological CBR temperature, Tγ(COBE) = 2.72548 ± 0.00057 K. These new results and CN fluorescence lifetime data are shown to give similar derived values for improved HL corrections as well as providing further evidence for the intramolecular coupling between the relevant B 2Σ+ state rotational levels and close-lying levels of the A 2Π state which invalidates the standard HL factors. Revised HL factors may be required in future Tγ(CN) measurements, in particular in high-redshift sites, which cannot be studied by bolometric means.

Low temperature cavity ring down spectroscopy with off-axis alignment: application to the A- and γ-bands of O2 in the visible at 90 K

The cavity ring down (CRD) technique presented here involves an optical cavity attached to a cryostat. The static cell and mirrors of the optical cavity are all inside a vacuum chamber at the same temperature of the cryostat. The temperature of the cell can be changed between 77 K and 298 K. An off-axis alignment of the laser beam into the cavity is used to increase the number of resonant modes inside the cavity and improve the signal to noise ratio of the absorption bands. To demonstrate the capabilities of the low temperature CRD cell, the absorption spectra of O2 are recorded at 90 K for the A (υ′=0←υ″=0) and γ (υ′=2←υ″=0) bands of the \(b^{1}\sum_{g}^{ +}\leftarrow X^{3}\sum_{g}^{ -} \) transition using cavity ring down spectroscopy. The optical cavity performance was tested using two variations of the CRD technique. The A-band is measured using the phase-shift cavity ring down method and the γ-band using the pulsed-laser exponential-decay method. A comparison between experimental and simulated spectra of the O2 bands at 90 K confirms the molecular temperature measured by a sensor localized in the cell. Quantitative measurements of the individual rotational line intensities are made for the oxygen γ-band to confirm the temperature of the cell and calculate the vibrational band intensity. The application of this technique for laboratory studies of planetary atmospheres and the spectroscopy of molecular complexes is emphasized.

Communication: A new spectroscopic window on hydroxyl radicals using UV + VUV resonant ionization

A 1 + 1' multiphoton ionization (MPI) detection scheme for OH radicals is presented. The spectroscopic approach combines initial excitation on the well-characterized A(2)Σ(+)-X(2)Π band system with vacuum ultraviolet (VUV) ionization via autoionizing Rydberg states that converge on the OH(+) A(3)Π ion state. Jet-cooled MPI spectra on the (1,0) and (2,0) bands show anomalous rotational line intensities, while initial excitation on the (0,0) band does not lead to detectable OH(+) ions. The onset of ionization with the (1,0) band is attributed to an energetic threshold; the combined UV + VUV photon energies are above the first member of the autoionizing (A(3)Π)nd Rydberg series. Comparison of the OH 1 + 1' MPI signal with that from single photon VUV ionization of NO indicates that the cross section for photoionization from OH A(2)Σ(+), v' = 1 is on the order of 10(-17) cm(2).

THE FLUORESCENCE EFFICIENCIES OF THE CN VIOLET BANDS IN COMETS

We have carried out calculations of the fluorescent equilibrium of the CN molecule in the solar radiation field as a function of heliocentric radial velocity and distance. The detailed rotational line intensities of the CN violet 0–0 band have been recalculated for radial velocities between −60 and +60 km s −1 and at 10 distances in steps of √ 2 from 0.25 to 5.7 AU. Comparisons with observed CN violet 0–0 band profiles yield reasonable agreement and remaining discrepancies are well understood. Based on the derived equilibrium rotational level populations of the ground state, 1–1 band rotational line intensities were also calculated. Total band fluorescence efficiencies for the violet Δν = 0 sequence are tabulated for the above range of distances and velocities, permitting the interpolation to any given comet’s observational circumstances. These fluorescence efficiencies, L/N ,o r “g-factors,” needed to reduce CN emission band fluxes to CN abundances, are also accessible via a Web-based service. The values at any heliocentric distance vary by about a factor of two with varying velocities, but the specific structure of this variation with velocity changes dramatically with distance.

Rotational analysis and line intensities of the HCO B̃2A′-X2A′311 band at 296 K

This paper computes the rotational energy levels of the HCO B̃2A′-X2A′ transition, especially, the higher values of the rotational quantum numbers NKaKc and Ka, with the rotational constants which are obtained via B3LYP method with 6–311G basis set, and the results show that the calculated frequencies using the computed vibration-rotation energy levels are in reasonable agreement with the data from the experiment. Meanwhile, the line intensities of HCO are first reported, the results are of significance for the studying HCO.