Molecules containing one or a few hydrogen atoms and a heavier atom (hydrides) have been predicted to trace FUV radiation. In some chemical models, FUV emission by the central object or protostar of a star forming region greatly enhances some of the hydride abundances. Two massive regions, W3 IRS5 and AFGL 2591, have been observed in hydride lines by HIFI onboard the {\it Herschel Space Observatory}. We use published results as well as new observations of CH$^+$ towards W3 IRS5. Molecular column densities are derived from ground state absorption lines, radiative transfer modeling or rotational diagrams. Models assuming no internal FUV are compared with two-dimensional models including FUV irradiation of outflow walls. We confirm that the effect of FUV is clearly noticeable and greatly improves the fit. The most sensitive molecules to FUV irradiation are CH$^+$ and OH$^+$, enhanced in abundance by many orders of magnitude. Modeling in addition also full line radiative transfer, Bruderer et al (2010b) achieve good agreement of a two-dimensional FUV model with observations of CH$^+$ in AFGL 2591. It is concluded that CH$^+$ and OH$^+$ are good FUV tracers in star-forming regions.

`Water In Star-forming regions with Herschel' (WISH) is a key program on the Herschel Space Observatory designed to probe the physical and chemical structure of young stellar objects using water and related molecules and to follow the water abundance from collapsing clouds to planet-forming disks. About 80 sources are targeted covering a wide range of luminosities and evolutionary stages, from cold pre-stellar cores to warm protostellar envelopes and outflows to disks around young stars. Both the HIFI and PACS instruments are used to observe a variety of lines of H2O, H218O and chemically related species. An overview of the scientific motivation and observational strategy of the program is given together with the modeling approach and analysis tools that have been developed. Initial science results are presented. These include a lack of water in cold gas at abundances that are lower than most predictions, strong water emission from shocks in protostellar environments, the importance of UV radiation in heating the gas along outflow walls across the full range of luminosities, and surprisingly widespread detection of the chemically related hydrides OH+ and H2O+ in outflows and foreground gas. Quantitative estimates of the energy budget indicate that H2O is generally not the dominant coolant in the warm dense gas associated with protostars. Very deep limits on the cold gaseous water reservoir in the outer regions of protoplanetary disks are obtained which have profound implications for our understanding of grain growth and mixing in disks.

The Herschel Space Observatory opens the sky for observations in the far infrared at high spectral and spatial resolution. A particular class of molecules will be directly observable; light diatomic hydrides and their ions (CH, OH, SH, NH, CH+, OH+, SH+, NH+). These simple constituents are important both for the chemical evolution of the region and as tracers of high-energy radiation. If outflows of a forming star erode cavities in the envelope, protostellar far UV (FUV; 6 < E_gamma < 13.6 eV) radiation may escape through such low-density regions. Depending on the shape of the cavity, the FUV radiation then irradiates the quiescent envelope in the walls along the outflow. The chemical composition in these outflow walls is altered by photoreactions and heating via FUV photons in a manner similar to photo dominated regions (PDRs). In this work, we study the effect of cavity shapes, outflow density, and of a disk with the two-dimensional chemical model of a high-mass young stellar object introduced in the second paper in this series. We find that the shape of the cavity is particularly important in the innermost part of the envelope, where the dust temperatures are high enough (> 100 K) for water ice to evaporate. If the cavity shape allows FUV radiation to penetrate this hot-core region, the abundance of FUV destroyed species (e.g. water) is decreased. In particular, diatomic hydrides and their ions CH$+, OH+ and NH+ are enhanced by many orders of magnitude in the outflow walls due to the combination of high gas temperatures and rapid photodissociation of more saturated species. The enhancement of these diatomic hydrides is sufficient for a detection using the HIFI and PACS instruments onboard Herschel. The effect of X-ray ionization on the chemistry is found to be small, due to the much larger luminosity in FUV bands compared to X-rays.

The Heterodyne Instrument for the Far Infrared (HIFI) onboard the Herschel Space Observatory allows the first observations of light diatomic molecules at high spectral resolution and in multiple transitions. Here, we report deep integrations using HIFI in different lines of hydrides towards the high-mass star forming region AFGL 2591. Detected are CH, CH+, NH, OH+, H2O+, while NH+ and SH+ have not been detected. All molecules except for CH and CH+ are seen in absorption with low excitation temperatures and at velocities different from the systemic velocity of the protostellar envelope. Surprisingly, the CH(J(F,P) = 3/2(2),(-) - 1/2(1,+)) and CH+(J = 1-0, J = 2-1) lines are detected in emission at the systemic velocity. We can assign the absorption features to a foreground cloud and an outflow lobe, while the CH and CH+ emission stems from the envelope. The observed abundance and excitation of CH and CH+ can be explained in the scenario of FUV irradiated outflow walls, where a cavity etched out by the outflow allows protostellar FUV photons to irradiate and heat the envelope at larger distances driving the chemical reactions that produce these molecules.

Context. Hydrides of the most abundant heavier elements are fundamental molecules in cosmic chemistry. Some of them trace gas irradiated by UV or X-rays. Aims. We explore the abundances of major hydrides in W3 IRS5, a prototypical region of high-mass star formation. Methods. W3 IRS5 was observed by HIFI on the Herschel Space Observatory with deep integration (� 2500 s) in 8 spectral regions. Results. The target lines including CH, NH, H3O + , and the new molecules SH + ,H 2O + ,a nd OH + are detected. The H2O + and OH + J = 1−0 lines are found mostly in absorption, but also appear to exhibit weak emission (P-Cyg-like). Emission requires high density, thus originates most likely near the protostar. This is corroborated by the absence of line shifts relative to the young stellar object (YSO). In addition, H2O + and OH + also contain strong absorption components at a velocity shifted relative to W3 IRS5, which are attributed to foreground clouds. Conclusions. The molecular column densities derived from observations correlate well with the predictions of a model that assumes the main emission region is in outflow walls, heated and irradiated by protostellar UV radiation.

Observations of CO+ suggest column densities on the order 10^12 cm^-2 that can not be reproduced by many chemical models. CO+ is more likely to be destroyed than excited in collisions with hydrogen. An anomalous excitation mechanism may thus have to be considered when interpreting CO^+ observations. Chemical models are used to perform a parameter study of CO^+ abundances. Line fluxes are calculated for N(CO+)=10^12 cm^-2 and different gas densities and temperatures using a non-LTE escape probability method. The chemical formation and destruction rates are considered explicitly in the detailed balance equations of the radiative transfer. In addition, the rotational levels of CO+ are assumed to be excited upon chemical formation according to a formation temperature. It is found, that chemical models are generally able to produce high fractional CO+ abundances (x(CO+) =10^-10). In a far-ultraviolet (FUV) dominated environment, however, high abundances of CO+ are only produced in regions with a Habing field G0 > 100 and T(kin) > 600 K, posing a strong constraint on the gas temperature. For gas densities >10^6 cm^-3 and temperatures > 600 K, the combination of chemical and radiative transfer analysis shows little effect on intensities of CO+ lines with upper levels N_up <= 3. Significantly different line fluxes are calculated with an anomalous excitation mechanism, however, for transitions with higher upper levels and densities >10^6 cm ^ -3. The Herschel Space Observatory is able to reveal such effects in the terahertz wavelength regime. Ideal objects to observe are protoplanetary disks with densities 10^6 cm^-3. It is finally suggested that the CO+ chemistry may be well understood and that the abundances observed so far can be explained with a high enough gas temperature and a proper geometry.

We aim to obtain accurate rate coefficients for the collisional excitation of CH+ by He for high gas temperatures. The ab initio coupled-cluster [CCSD(T)] approximation was used to compute the interaction potential energy. Cross sections are then derived in the close coupling (CC) approach and rate coefficients inferred by averaging these cross sections over a Maxwell-Boltzmann distribution of kinetic energies. Cross sections are calculated up to 10'000 cm^-1 for J ranging from 0 to 10. Rate coefficients are obtained at high temperatures up to 2000 K.

Aims. The aim is to probe high energy radiation emitted by deeply embedded protostars.Methods. Submillimeter lines of CN, NO, CO+ and SO+, and upper limits on SH+ and N2O are observed with the James Clerk Maxwell Telescope in two high-mass and up to nine low-mass young stellar objects and compared with chemical models.Results. Constant fractional abundances derived from radiative transfer modeling of the line strengths are x( CN) approximate to a few x 10(-11) - 10(-8), x(NO) approximate to 10(-9) - 10(-8) and x(CO+) approximate to 10(-12) - 10(-10). SO+ has abundances of a few x 10(-11) in the high-mass objects and upper limits of approximate to 10(-12) - 10(-11) in the low-mass sources. All abundances are up to 1 - 2 orders of magnitude higher if the molecular emission is assumed to originate mainly from the inner region ( less than or similar to 1000 AU) of the envelope. For high-mass sources, the CN, SO+ and CO+ abundances and abundance ratios are best explained by an enhanced far-ultraviolet (FUV) field impacting gas at temperatures of a few hundred K. The observed column densities require that this region of enhanced FUV has scales comparable to the observing beam, such as in a geometry in which the enhanced FUV irradiates outflow walls. For low-mass sources, the required temperatures within the FUV models of T greater than or similar to 300 K are much higher than found in models, so that an X-ray enhanced region close to the protostar ( r less than or similar to 500 AU) is more plausible. Gas-phase chemical models produce more NO than observed, suggesting an additional reduction mechanism not included in current models.Conclusions. The observed CN, CO+ and SO+ abundances can be explained with either enhanced X-rays or FUV fields from the central source. High-mass sources likely have low opacity regions that allow the FUV photons to reach large distances from the central source. X-rays are suggested to be more effective than FUV fields in the low-mass sources. The observed abundances imply X-ray fluxes for the Class 0 objects of L-X approximate to 10(29) - 10(31) erg s(-1), comparable to those observed from low-mass Class I protostars. Spatially resolved data are needed to clearly distinguish the effects of FUV and X-rays for individual species.

Context. The chemistry in the inner few thousand AU of accreting envelopes around young stellar objects is predicted to vary greatly with far-UV and X-ray irradiation by the central star. Aims. We search for molecular tracers of high-energy irradiation by the protostar in the hot inner envelope. Methods. The Submillimeter Array (SMA) has observed the high-mass star forming region AFGL 2591 in lines of CS, SO, HCN, HCN(v(2) = 1), and (HCN)-N-15 with 0.6" resolution at 350 GHz probing radial scales of 600-3500 AU for an assumed distance of 1 kpc. The SMA observations are compared with the predictions of a chemical model fitted to previous single-dish observations. Results. The CS and SO main peaks are extended in space at the FWHM level, as predicted in the model assuming protostellar X-rays. However, the main peak sizes are found smaller than modeled by nearly a factor of 2. On the other hand, the lines of CS, HCN, and (HCN)-N-15, but not SO and HCN(v(2) = 1), show pedestal emissions at radii less than or similar to 3500 AU that are not predicted. All lines except SO show a secondary peak within the approaching outflow cone. A dip or null in the visibilities caused by a sharp decrease in abundance with increasing radius is not observed in CS and only tentatively in SO. Conclusions. The emission of protostellar X-rays is supported by the good fit of the modeled SO and CS amplitude visibilities including an extended main peak in CS. The broad pedestals can be interpreted by far-UV irradiation in a spherically non-symmetric geometry, possibly comprising outflow walls on scales of 3500-7000 AU. The extended CS and SO main peaks suggest sulfur evaporation near the 100 K temperature radius. The effects of the corresponding abundance jumps may be reduced in visibility plots by smoothing due to inhomogeneity at the evaporation radius, varying by +/- 10% or more in different directions.

High-resolution spectra of the Spitzer Space Telescope show vibration-rotation absorption bands of gaseous C2H2, HCN, and CO2 molecules toward a sample of deeply obscured (U)LIRG nuclei. The observed bands reveal the presence of dense (n ≳ 107 cm-3), warm (Tex = 200-700 K) molecular gas with high column densities of these molecules ranging from a few 1015 to 1017 cm-2. Abundances relative to H2, inferred from the silicate optical depth, range from ~10-7 to 10-6 and show no correlation with temperature. Theoretical studies show that the high abundances of both C2H2 and HCN exclude an X-ray dominated region (XDR) associated with the toroid surrounding an AGN as the origin of this dense warm molecular gas. Galactic massive protostars in the so-called hot-core phase have similar physical characteristics with comparable high abundances of C2H2, HCN, and CO2 in the hot phase. However, the abundances of C2H 2 and HCN and the C2H2/CO2 and HCN/CO2 ratios are much higher toward the (U)LIRGs in the cooler (Tex ≲ 400 K) phase. We suggest that the warm dense molecular gas revealed by the mid-IR absorption lines is associated with a phase of deeply embedded star formation, where the extreme pressures and densities of the nuclear starburst environment have inhibited the expansion of H II regions and the global disruption of the star-forming molecular cloud cores and have "trapped" the star formation process in an "extended" hot-core phase.