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Stewart, 22, said that after Twilight's innocent Bella, baring it all as the uninhibited Marylou for giddy depictions of free love in the screen adaptation of Jack Kerouac's classic novel had been a breath of fresh air.
"I love pushing, I love scaring myself. I think to watch genuine experience on screen is just so much more interesting," the Los Angeles-born star told reporters.
'Very vivid'
"The reason I wanted to do the job is because, you know, you read something, you're provoked on some level and then it's just taking that further and being able to live it and I always want to get as close to the experience as I possibly can.
"As long as you're always being really honest, there's nothing ever to be ashamed of."
On the Road, Kerouac's autobiographical tale about his wandering years in the late 1940s and early 1950s, presents his alter ego Sal Paradise, who is mesmerised by a charismatic drifter called Dean Moriarty.
Stewart, who also appeared in Sean Penn's Into the Wild, plays Moriarty's free-spirited and outspoken wife who becomes his long-time mistress after they divorce while she carries on dalliances with Paradise and others.
"Obviously I love Marylou - the character is very vivid and she jumps right off the page, she smacks you in the face, you know, with her tongue," she said.
She noted that the women in the story get more attention in the film than in the novel and said that one can see Marylou, who leaves the carousing Moriarty to marry a sailor, as the picture's central figure.
"She's so completely human, she never made herself a commodity. If you were to choose one character that really, truly embodied the spirit of this book it was her," she said.
Stewart drew generally positive reviews after a politely received screening of the film, with movie industry website Indiewire saying that "seeing her liberated from the silly straitjacket of servile moping she has to perform in the Twilight films is a huge relief".
On the Road is up against 21 other films for the festival's coveted Palme d'Or top prize including David Cronenberg's Cosmopolis starring Stewart's on- and off-screen partner Robert Pattinson.
Watch the One the Road trailer here:
