Answer
This points to the mail server's TLS certificate chain not being trusted by the Java runtime IFS's mail-sending component uses — export the SMTP provider's certificate (via a browser, viewing the site's certificate) and import it into that Java runtime's trust store using keytool -import -trustcacerts -keystore <path-to-cacerts> -storepass changeit (with an alias identifying your environment), then retry sending mail; a missing intermediate or root CA certificate in the trust store used by the specific process making the SMTP connection is a common cause of this exact PKIX-path error even when every other mail-sender setting is correct.