Getting married to US citizen alone does not make her a US citizen. Your brother needs to file a petition to adjust her status or simply known as green card, then she will be eligible to obtain SSN and driver's license.
If she does not have these 3 items, finding a job would be very difficult especially in some states such as AZ or CA where employers are required to run a background check and verify legal status before hiring. If she doesn't have any connection, the chance to get a job is very slim.
If they were married but her husband failed to file petition to adjust status for her, she's still illegal.
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