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Self-affirmation theory posits that people are motivated to maintain a positive self-view and that threats to perceived self-competence are met with resistance. When threatened, self-affirmations can restore self-competence by allowing individuals to reflect on sources of self-worth, such as core values. Many questions exist, however, about the underlying mechanisms associated with self-affirmation. We examined the neural mechanisms of self-affirmation with a task developed for use in a functional magnetic resonance imaging environment. Results of a region of interest analysis demonstrated that participants who were affirmed (compared with unaffirmed participants) showed increased activity in key regions of the brain’s self-processing (medial prefrontal cortex + posterior cingulate cortex) and valuation (ventral striatum + ventral medial prefrontal cortex) systems when reflecting on future-oriented core values (compared with everyday activities). Furthermore, this neural activity went on to predict changes in sedentary behavior consistent with successful affirmation in response to a separate physical activity intervention. These results highlight neural processes associated with successful self-affirmation, and further suggest that key pathways may be amplified in conjunction with prospection.