When the construction "ti" is followed by a vowel, the "t" becomes an "s" as long as the "t" does not occur at the begining of the word.
In your example, "diplomatie," the letter "t" is not at the beginning of the word, and it is followed by an i and then a vowel. The "t" is pronounced as an "s."
Examples:
Alternative : pronounced as a "t" because the "ti" is followed by the consonant "v," not by a vowel
Attention: The "tion" is pronounced with an "s" sound, not a "t"
Patient: The "tient" is pronounced with an "s" sound at the beginning, not a "t"
Superstitieux: The "tieux" is pronounced with an "s" sound, not a "t"
But at the beginning of a word, a "ti" retains the "t" sound, even if followed by a vowel.
Examples:
Tiede, un tiers, tiens, le tien, la tienne
So in your example, "diplomatie," the "a" is not relevant, except that *something* comes before the "tie." The "tie" is not at the beginning of a word.
As with all rules, expect exceptions.