Last time I tried configuring a Linux-hosted PHP to do SMTP on localhost:25 instead of shelling out to call sendmail, I found that only Windows builds even have that functionality compiled in. You can apply the same configuration options on a stock Linux build, and they won't cause errors, but they won't do anything, either. Maybe that's changed recently, but it would have to have been very recently, because I ran into this (for the umpteenth time) just a few months ago, while reworking my team's dev environment to allow for examining sent mail without requiring heroism.
I'm not a PHP hater, exactly. I don't like the language at all, but I understand it well and have made a very good living based partly on that knowledge. But the mail story in PHP has never not been a dumpster fire.
[0] http://windows.php.net/