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→By public transport and hitchhiking
Both companies have Facebook pages, in Spanish, where they publish their bus timetables
If you miss your bus to the national park and are short of time, you can hitchhike from Valdesina, which is a small settlement that is located on the road between Molina and Radal. You can take a minibus or ("micro") to Valdesina. These minibuses leave from Curicó bus terminal and make a stop at Molina bus terminal on the way. It's just a case of riding the minibus one of them as far as it will take you once you get beyond Molina, and then getting off the minibus before it turns around and goes back the other way. If you can't find a minibus with a "Valdesina" destination sign on its front, then just hop on one that has a "Tres Esquinas" sign on the windscreen. Provided you ride it all the way to the end, a Tres Esquinas minibus will take you almost as far up the Molina-Radal road as the Valdesina ones do.
Bear in mind that if you are visiting the national park outside of the peak tourist season -- even in the BEST case scenario, you will have to hitchhike into it from Radal village, at the very least.