Gunpowder warfare is being fought daily on MTW/VI! It is Napoleonic Total War (NTW). I haven't play the latest version of it, but I think it has plenty of gunpowder :)
Totalwar is suitable to formational warfare. Modern warfare, due to increased fire power, it is a zone warfare. "If you see the enemy, you are dead". Troops advance in dispersed formation, etc.
That being said, it is imaginable to mod the game so that a game's unit represents, say a tank company of 14 tanks (US tank unit). They would advance in formation, etc. Difficulties is to represent the other aspects of modern warfare. Without the counter balance of infantry, artillery cover, anti-tank mines, aero support, tanks would reign supreme and it would make a very boring game. So I suggest we stick at formational warfare: the latest you can go is perhaps american civil war.
In formational warfare with gunpowder, guns became more important, but still not have the range and accuracy, firing rate, of modern guns. The importance of morale and concentration of fire is still important, so going together in formation actually increase your chance of survival (something very hard to grasp for us modern people, "gosh, why do you advance in line, stand and shoot, it is crazy!").
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