Emotional coordination is a core property of human interaction that shapes how relational meaning is constructed in real time. While text-based affect inference has become increasingly feasible, prior approaches often treat sentiment as a deterministic point estimate for individual speakers, failing to capture the inherent subjectivity, latent ambiguity, and sequential coupling found in mutual exchanges. We introduce LLM-MC-Affect, a probabilistic framework that characterizes emotion not as a static label, but as a continuous latent probability distribution defined over an affective space. By leveraging stochastic LLM decoding and Monte Carlo estimation, the methodology approximates these distributions to derive high-fidelity sentiment trajectories that explicitly quantify both central affective tendencies and perceptual ambiguity. These trajectories enable a structured analysis of interpersonal coupling through sequential cross-correlation and slope-based indicators, identifying leading or lagging influences between interlocutors. To validate the interpretive capacity of this approach, we utilize teacher-student instructional dialogues as a representative case study, where our quantitative indicators successfully distill high-level interaction insights such as effective scaffolding. This work establishes a scalable and deployable pathway for understanding interpersonal dynamics, offering a generalizable solution that extends beyond education to broader social and behavioral research.