There is no way.
SmtpClient bascially can not validate the usernamepassword without contacting the serve it connects to.
What you could do is do it outside SmtpClient, by opening a TCP connection to the server… but authentication CAN be complicated depending how the server is configured.
May I ask WHY you need to know that before sending? normal behavior IMHO would be to wrap sending in appropriate error handling to catch exceptions here.