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Aims.The goal is to develop a database of rate coefficients for rotational state-to-state transitions in H₂O + H₂O collisions that is suitable for the modeling of energy transfer in nonequilibrium conditions, in which the distribution of rotational states of H₂O deviates from local thermodynamic equilibrium. Methods.A two-temperature model was employed that assumed that although there is no equilibrium between all possible degrees of freedom in the system, the translational and rotational degrees of freedom can be expected to achieve their own equilibria independently, and that they can be approximately characterized by Boltzmann distributions at two different temperatures,T_kinandT_rot. Results.Upon introducing our new parameterization of the collisional rates, taking into account their dependence on bothT_kinandT_rot, we find a change of up to 20% in the H₂O rotational level populations for both ortho and para-H₂O for the part of the cometary coma where the nonequilibrium regime occurs. 

Abstract We report a comprehensive study of the cyanopolyyne chemistry in the prototypical prestellar core L1544. Using the 100 m Robert C. Byrd Green Bank Telescope, we observe three emission lines of HC₃N, nine lines of HC₅N, five lines of HC₇N, and nine lines of HC₉N. HC₉N is detected for the first time toward the source. The high spectral resolution (∼0.05 km s⁻¹) reveals double-peak spectral line profiles with the redshifted peak a factor 3–5 brighter. Resolved maps of the core in other molecular tracers indicate that the southern region is redshifted. Therefore, the bulk of the cyanopolyyne emission is likely associated with the southern region of the core, where free carbon atoms are available to form long chains, thanks to the more efficient illumination of the interstellar field radiation. We perform a simultaneous modeling of the HC₅N, HC₇N, and HC₉N lines to investigate the origin of the emission. To enable this analysis, we performed new calculation of the collisional coefficients. The simultaneous fitting indicates a gas kinetic temperature of 5–12 K, a source size of 80″, and a gas density larger than 100 cm⁻³. The HC₅N:HC₇N:HC₉N abundance ratios measured in L1544 are about 1:6:4. We compare our observations with those toward the well-studied starless core TMC-1 and with the available measurements in different star-forming regions. The comparison suggests that a complex carbon chain chemistry is active in other sources and is related to the presence of free gaseous carbon. Finally, we discuss the possible formation and destruction routes in light of the new observations.