In some cases your PHP application should already have the option built in to use SMTP authentication instead of the default PHP mail() function. If this is the case then you can go ahead and simply fill in your details for your Google Apps account in that section.
If your application doesn't have this built in already, then you would need to set this up somehow in your PHP code to allow for remote SMTP connections.
A very common method used is the PHPMailer class available at:
PHPMailer - Full Featured Email Transfer Class for PHP
Then you would load up that class in your PHP script and utilize it with something along these lines:
I hope that information answered your question. If you have any further questions at all please feel free to ask away!
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