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Peace of mind is a colloquialism that refers to a state of being mentally or spiritually at peace, with enough knowledge and understanding to keep onself strong in the face of discord or stress. Having "peace of mind" or being "at peace" is considered to be healthy —the opposite of being under stress or anxious.
Peace of mind, serenity, calmness, etc., are descriptors of a disposition free from the effects of stress, and in some cultures such a disposition is considered a state of mind that may be cultivated by various forms of training. See: meditation, T'ai Chi Ch'uan, yoga.