Yes. Not in your assessment of whether any college team would win against the U.S. or Canadian Olympic teams; if anything, your estimate of 1 time in 5 is high. It's your analysis of why that's true that's very, very wrong.
It has nothing to do with declining talent in the game. It's that there are two of those teams who select the best players from among 35 Division 1 teams, with no arbitrary limit of how many years each of those players can remain on the team. The national teams are much better, because they are selecting vastly fewer players from a much larger pool of talent. That's true whether or not any of the leagues they play in can really be considered professional. Minnesota would be a much better team if Lee Stecklein and Dani Cameranesi hadn't run out of eligibility.
There aren't as many current NCAA players on the national team rosters as there used to be, but that's not really surprising. The human body doesn't fully mature until your mid-20s, so athletes are improving physically even after they've left college, as well as gaining more experience. Even after one's physical peak, the decline starts slowly and experienced is still gained. The mix varies from one sport to the next, but a hockey player's peak ability is somewhere in the mid-to-late 20s. (It's probably a bit earlier for women relative to men, and it's a bit later for defensemen relative to forwards.) As the talent pool of women's hockey players has expanded, there are more national team caliber players in this older age group, and fewer current NCAA players that can compete with them right now, but that will as they age towards their peak.
