Unix paths are nul-byte-terminated, so UTF-16 generally doesn't make any sense in this context. Valid Unicode paths are encoded as UTF-8 on unix systems. UTF-16 and UTF-32 are invalid ways to encode Unicode paths. (That's not to say no one has tried to do it, just that it doesn't make any sense.)

(As other commenters have pointed out, Unix paths do not require a specific encoding, so robust applications cannot rely on any assumptions about encoding of existing files. But when creating new files, they must not try to encode paths as UTF-16.)