How to use the sunrise.php script for Multisite network domain mapping?

As per the instructions for setting up WordPress MU Domain Mapping, sunrise.php needs to be placed directly in your /wp-content directory. It’s not a plugin in the traditional sense, so can’t be placed in mu-plugins (or even plugins for that matter).

Setting up this plugin can take a bit of manual work so take care to follow the instructions carefully, including the modifications you need to make to wp-config.php.

By the way, the current status of this plugin is somewhat unclear as – for new sites – it appears its functionality is now baked in to WordPress core. It is (apparently) only now required for pre-existing Multisites which were converted some time ago. You can see various posts from the maintainer of the plugin in this support forum which confirm this.