Only medical doctors (MD's) and psychologists with doctoral degrees in clinical psychology (PhD's) can diagnose mental disorders such as post traumatic stress disorder (PTSD). And with medical doctors (MD's), psychiatrists are specialists who have expertise in diagnosing and treating mental disorders, such as PTSD. If you want an assessment for a mental disorder such as PTSD, the professional with the most expertise in diagnosing and treating PTSD are psychiatrists.
But not all PhD psychologists can diagnose mental disorders such as PTSD. Only psychologists with a PhD in clinical psychology can diagnose mental disorders such as PTSD.