Would you say that Lawful Neutral is the most "libertarian" alignment?
And I think true neutral would be Libertarian, lawful would obey all laws, like ones on weed

Naw. Chaotic good is the closest thing to a libertarian alignment. Do the right thing, fuck rules and rule makers and
FUCK THE MAN.
I played a character that was different than I am in real life, because doing something different than what you know and are is sorta the whole point of role playing/acting/make pretend.
Originally I played Hexus as "Neutral selfish", which is a jokey version of neutral evil. (It said neutral evil on his character sheet) He could generally be trusted but when a Big Bad occasionally threw out the inevitable offer of "Betray your friends and join me MWAHAHA" everyone would turn and look at me expectantly and I'd say "WHAT?!?!" but of course he would never betray his peeps.
After about five years of playing him that way he had a change of heart over several serious events. Had to take the XP hit for an alignment change.
Of course he was the comic relief character of the group so he never got
too serious. Hexus was probably the only character in D&D history who:
1. Sold snake oil out of a wagon, only the snake oil was a phylactary and potion pre made to turn someone into a Lich. (DRINK THE JUICE AND LIVE FOREVER, YEAH, SOME BITS'LL FALL OFF BUT WHATEVS)
2. Teleported himself onto the back of a (Flying) Great Wyrm white dragon and cast Abi Dalzim's Horrid Wilting on it. (S'a badass spell and did 22d8+some metamagic damage.) Spell does damage by sucking all the water out of an area of effect, turning living things into beef jerky. He then proceeded to ride the now very dead dragon all the way down to the ground, climb out of the splattered mess, and yell "THE GODS ARE ALL CHILDREN AND I DARE ONE TO STRIKE ME DOWN!!!" while dancing "A little jig"
3. (Toward retirement obviously) Had an army (60,000 troops) of friendly talking skeletons.
4. Owned a huge,
nine towered magic university (For all the different alignments so there'd be no horseplay in the dining room) that he one day up and decided to dig out of the ground and slap 12 Spelljamming furnaces into so he could tool around in a floating/flying magic school. It was half a mile across and blotted out the sun. Occasionally caused misunderstandings when he'd noodle into town.
5. Was married to a high priestess of Loviatar, Mistress of Pain. They basically acted like the Addams family, affable and friendly but lots of skeleton motif shit and skeletal servants and putting each other on the rack all that sorta jazz.
6. Had a kid who died at the age of five from an illness. They bound his soul to a skeleton so he could stick around. Was Hexus's wacky snarky sidekick on adventures.
7. Accidentally destroyed a fair chunk of downtown Waterdeep, made reparations with Blackstaff (Head Wizard in charge over there) and so annoyed through attitude, then flipped him an extra gold coin and winked at him, that this 30 oddish level archmage mayor president governor bossman chased him through the streets wacking him with a staff screaming for him never to return.
So anyway yeah, Chaotic Good is libertarian.