I've never had a problem flying corporate with former fighter jocks. The owner of my company is a prior Army Commander that loves having us Air Force types around. Sometimes the owner thinks we are the only people in the company that understand him. The flight department is a relaxed but tightly run atmosphere he retreats to when he wants to get away from other corporate drama.
As for being on call 24/7, life is an adventure. I'm on call 24/7, and when the handful of times I get called with minimal notice happens, I'm excited for the adventure. I'm always sober and ready to go. if something important is coming up for me, I'll give them a few weeks notice. In two years, I've had one scheduling conflict. The winner is always the company. You get a lot of free time in most corporate jobs. Don't waste it. Spend it on your loved ones and make sure they care and understand when you miss something important. Standard life rules for any hardworking professional, if you ask me. It's far easier on my family than the military ever was. I wont complain about having time off but being on call when my friends at the regionals just assume they will be completely gone 6 days a week.