I don't know if this is irrational, but when I offer someone a job and they try to negotiate the salary it makes me want to instantly withdraw the offer. I have not had good experiences with employees who do this.
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Why though? If you were on the other side, would you not ask?
Well...I want to withdraw it because I've had bad experiences with people who've done that. Could be me. Could be a weird sample. As a buyer of goods, I almost always ask. However, employment is relationship oriented, and not transactional. Also, depends on small or big company.