Some people are far more comfortable and fluid in formal situations where the relationship between the two people is clearly defined and the reasons for the interaction are clearly defined.
Since the job is about work that makes the agenda clear and there is no anxiety about "what to talk about."
In a job interview there is no anxiety about, "Does this person want to talk to me? Am I wasting his/her time? Is she bored?"
It's also the fact that you feel qualified for the job whereas in a normal situation you don't necessarily feel qualified to be the person's friend or acquaintance or boyfriend/girlfriend, etc.
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