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Season 2, Episode 12 (aired 7 january 2005) was titled "Game Theory." During a drawn-out game of rock paper scissors, one character reasons:

As the probability of duplicating a tie decreases with each tie thrown, human behavior becomes the deciding factor. This is the domain of the philosophers and the poets and not the mathematicians.

A lengthy discussion of game theory's virtues follows. The episode contains another reference in the context of rock-paper-scissors to behavioral models:

Glynis: Perhaps it's the psychology she's using, not algebra. You know, rock is id, paper--ego, scissor--superego.
Grace: You people are seriously warped. It's a game. It's about luck.
Luke: No, grace. Games are never about luck. Everything has a strategy from government to romance, such as the time when I gave you a gift-- a calculated gambit designed to throw you in a state of imbalance.
Grace: You worked me?
Luke: No, no.
Grace: You used a gambit on me?!
Luke: No, grace. I'm making an analogy.
Friedman: That was some bad math, dude.

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Other relevant dialog follows:

Roger: Good. 'Cause that's what colleges want-- the real Joan.
Joan: What if I'm still trying to find out who that is?
Roger: Start by finding out what turns you on.
Joan: (she is awkward) Well...ha ha. Kicking geek rump at rock, paper, scissors was pretty sweet. Winning definitely turns me on.
Roger: A little militant, but... oh. (he puts a book in her hand)
Joan: Game theory? Art of war.
Roger: Sun Tzu. Kicking rump for more than 2,000 years.

While playing rock-paper-scissors:
Glynis: You have to find a way to take psychology out of the game.
Friedman: Following a predetermined gambit like the avalanche-- rock rock rock or the scissor sandwich, paper scissors paper.
Luke: Which takes the decision-making away from the player, giving us the advantage in a zero sum situation.
Glynis: Mathematical purity, statistical certainty. I have chills.
...
Friedman: (Wants to play) Ok, Girardi, 2 out of 3. Let's go.
Joan: Not now, toe jam.
Friedman: Ooh, scared. I guess she realizes that the analytical mind does in fact trump dumb luck.
Joan: Are you calling me dumb?
Friedman: Oh, excusez-moi. Intellectually challenged. Shall we dance?
Joan: Bring it.
Both: Rock, paper, scissors, shoot. (Friedman Wins) Rock, paper, scissors, shoot. (Joan wins) Rock, paper, scissors, shoot. (Friedman wins)
Friedman: Yes! Balance has been restored to the universe.
Joan: He's right. I am dumb.
Grace: Oh, easy, Girardi. It's a stupid kid's game.
Joan: Not to them. To them it's some bizarro math problem I'll probably never understand. Roger is such a poser. I can't believe what an idiot I've been.
Grace: Hey, pull up. The plane is spiraling out of control.
Joan: You know, I really wanted to be as smart as everyone else, but I'm not. You were right, Adam was right. I totally got scammed by roger.
Grace: Girardi!

Another day. Grace rushes to school hoping for a rematch:
Grace: Slow down. I'm losing weight.
Joan: I'm making a move.
Grace: Yeah, a fast one. What happened? I thought you crashed and burned.
Joan: It's because I wasn't playing. Other people were making the moves for me. I stayed up all night reading those books that Roger gave me on psychology, game theory. Do you realize that a player gives off a hint of aggression when he throws rock and there are strategies in the art of war--

At the high school, Luke and Friedman are playing

Luke, Friedman: Rock. Paper. Scissors. Shoot. Rock. Paper. Scissors. Shoot. Rock. Paper. Scissors. Shoot.
Glynis: This is so intense. Me next.
Joan: It's payback time.
Friedman: Joan, I'm sorry. We don't handicap players here.
Joan: Button it, fro-man. Let's play.
Grace: Flatten him, Girardi.
Luke: There's no reason for hostility here.
Joan: You're next, squidboy. You and your friends think I'm some kind of bonehead? Think again. Let's play. Ready?
Friedman: Yeah.

(There is a marching band playing in a class room near them.)

Friedman: Music's a little distracting--
Joan: well, not for me. 2 out of 3. Don't throw scissors.
Both: Rock. Paper. Scissors. Shoot. (Friedman throws a scissor and Joan a rock)
Joan: Told ya.
Both: Rock. Paper. Scissors. Shoot. (Friedman Wins) Rock. Paper. Scissors. Shoot. (Joan Wins)
Joan: Yes! Hey! Who's the bonehead now? Next?
Luke: Joan--
Luke: what. You think I'm some kind of idiot, huh? That it would just be easy to take me out?
Luke: I never said you were an idiot.
Joan: Yeah, but you let them say it.
Friedman: Just do it, man, redemption.
Joan: I'll cut you some slack, hmm? We'll play sets. 2 out of 3.
Luke: Why are you doing this?
Joan: 'Cause I wanna win. Just like you.

Both: Rock. Paper. Scissors. Shoot. (Luke wins)
Rock. Paper. Scissors. Shoot. (Tie)
Rock. Paper. Scissors. Shoot. (Tie again)
Rock. Paper. Scissors. Shoot. (Luke Wins)

Joan: Aah!

Grace: Focus. Don't lose it, Girardi.
Joan: I got it.
Luke: I thought you'd root for me, grace.
Grace - Make out with you, root for her.

Rock. Paper. Scissors. Shoot. (Luke Wins)
Rock. Paper. Scissors. Shoot. (Joan Wins)
Rock. Paper. Scissors. Shoot. (Joan Wins)

Joan: Yes! Ha ha ha!
Friedman: Last set. Last set. Up a notch.
Joan: Ahem.

Rock. Paper. Scissors. Shoot. (Tie)
Rock. Paper. Scissors. Shoot. (Tie)
Rock. Paper. Scissors. Shoot. (Tie)
Rock. Paper. Scissors. Shoot. (tie)

Friedman: Let's go. Let's go. You got it. You got it.
Joan: As the probability of duplicating a tie decreases with each tie thrown, human behavior becomes the deciding factor. This is the domain of the philosophers and the poets and not the mathematicians.
Friedman: That was so hot.

Rock. Paper. Scissors. Shoot. (Joan)
Rock. Paper. Scissors. Shoot. (Luke)
Rock. Paper. Scissors. Shoot. (tie)

Rock. Paper. Scissors. Shoot (Luke Wins)

Luke: Yes!

Joan: I thought I had-- I thought I had him.
Grace: You did. You did. You see how much you made him sweat? I can't even get him to do that when we're alone.
Glynis: Good try Joan

A full synopsis of this episode, written by Deborah, is available at televisionwithoutpity.com