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If certain skills are locked you need to put your XP in some other skills first to achieve the required levels.
/edit
Just took a little test spending XP on skills - looks like each level is 600 XP spend on skills.
Mesmerize is leveled by doing the main quest. You can't spend XP on it.
As an example Mesmerize II:
... is gained after the finishing the blackmail quest. Which is a bit odd - because you are supposed to be able to use Mesmerize II on someone during the main quest before you unlock it. Maybe an oversight.
If you go to bed, you need to spend your XP on skills first to level up. Click and hold mouse button (or appropriate button on controller) while selecting a skill. And then confirm.
And like Entity said: Your first skill to level up to 2 is Autophage. Then you have to pick one of the three offensive skills to get to level 3. And from there on it's getting more and more open because you unlock more options.