You will have to map the physicalPath to a virtualPath. Here is how you would do that.
using System.Web.Configuration; //Reference the System.Web DLL (project needs to be using .Net 4.0 full, not client framework)
public static Configuration OpenConfigFile(string configPath)
{
var configFile = new FileInfo(configPath);
var vdm = new VirtualDirectoryMapping(configFile.DirectoryName, true, configFile.Name);
var wcfm = new WebConfigurationFileMap();
wcfm.VirtualDirectories.Add("https://stackoverflow.com/", vdm);
return WebConfigurationManager.OpenMappedWebConfiguration(wcfm, "https://stackoverflow.com/");
}