Recent research shows that Large Language Models (LLMs) exhibit a compelling level of proficiency in Theory of Mind (ToM) tasks. This ability to impute unobservable mental states to others is vital to human social cognition and may prove equally important in principal-agent relations between individual humans and Artificial Intelligences (AIs). In this paper, we explore how a mechanism studied in developmental psychology known as Violation of Expectation (VoE) can be implemented to reduce errors in LLM prediction about users by leveraging emergent ToM affordances. And we introduce a \textit{metacognitive prompting} framework to apply VoE in the context of an AI tutor. By storing and retrieving facts derived in cases where LLM expectation about the user was violated, we find that LLMs are able to learn about users in ways that echo theories of human learning. Finally, we discuss latent hazards and augmentative opportunities associated with modeling user psychology and propose ways to mitigate risk along with possible directions for future inquiry.