Can I withdraw from an esop program if I'm 100% vested but I no longer work for the company?

Can I withdraw from esop account if I am know longer an employee

Maybe - it depends on whether you are (a) retired or became disabled (in which case you can withdraw our vested ESOP assets immediately), or (b) left the job for other reasons. If the latter - then you may have to wait as long as 6 years before you can withdraw assete from the ESOP - it all depends on the plan rules. I suggest you call your former employer and find out what the rules say.

For more information - here's a site that does a good job of explaining ESOP rules:
ESOP Vesting, Distribution, and Diversification Rules