I don't like either of them in a negative statement.
1. This is the emotion people want to experience most of all.
2. This is the emotion people want to experience more than anything.
These are both correct and equivalent in meaning. In the case of a negative, try:
1. This is the emotion people want to experience least of all. (a little better)
2. This is the emotion people want to experience less than anything anything else. (a little worse)



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