This is a FAQ. XPath considers any unprefixed name in an expression to belong to "no namespace".
Dmitre is right. You need to take a look at XML::LibXML::XPathContext which will allow you to declare the namespace and then you can use namespace aware XPath statements. I gave an example of using this some time ago on stackoverflow - have a look at Why should I use XPathContext with Perl's XML::LibXML.
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