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In staffing and recruitment, a unicorn refers to an imaginary person with a set of qualifications that are very unlikely to be found together, or would be prohibitively expensive to hire if found. For example, a job listing might specify:
DevOps Rockstar! * Extensive experience with Chef * In-depth experience with Linux packaging technologies * Experience developing training materials and leading training sessions * Windows automation experience * ETL background on AIX
Such a position would be very difficult to fill, because of personality incompatibilities (extroversion as typically present in trainers is less prevalent among packagers and automators) as well as unlikely career paths (few paths would touch on Windows, AIX, and Linux in-depth).
Because of the highly interdisciplinary nature of DevOps work, positions are often described as requiring odd mixes of technologies. Typically, a better solution is to split the position into two or more junior positions with skills that are easier to find.