We performed Herschel/HIFI observations of intermediate-excitation molecular lines in the far-infrared/submillimeter range in a sample of ten protoplanetary nebulae and young planetary nebulae. The high spectral resolution provided by HIFI yields accurate measurements of the line profiles. The observation of these high-energy transitions allows an accurate study of the excitation conditions, particularly in the warm gas, which cannot be properly studied from the low-energy lines. We have detected FIR/sub-mm lines of several molecules, in particular of 12CO, 13CO, and H2O. Emission from other species, like NH3, OH, H2^{18}O, HCN, SiO, etc, has been also detected. Wide profiles showing sometimes spectacular line wings have been found. We have mainly studied the excitation properties of the high-velocity emission, which is known to come from fast bipolar outflows. From comparison with general theoretical predictions, we find that CRL 618 shows a particularly warm fast wind, with characteristic kinetic temperature Tk >~ 200 K. In contrast, the fast winds in OH 231.8+4.2 and NGC 6302 are cold, Tk ~ 30 K. Other nebulae, like CRL 2688, show intermediate temperatures, with characteristic values around 100 K. We also discuss how the complex structure of the nebulae can affect our estimates, considering two-component models. We argue that the differences in temperature in the different nebulae can be due to cooling after the gas acceleration (that is probably due to shocks); for instance, CRL 618 is a case of very recent acceleration, less than ~ 100 yr ago, while the fast gas in OH 231.8+4.2 was accelerated ~ 1000 yr ago. We also find indications that the densest gas tends to be cooler, which may be explained by the expected increase of the radiative cooling efficiency with the density.
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