That build looks pretty good to me. Good synergy between skills I'm a fan of the Steady Aim and Archery as passives for PVE.
I like that you included rain of vengeance. I think it gets overlooked somewhat. I see a lot of potential for it on tough fights. It goes well with Frost arrow too, since Frost arrow is somewhat effective as both an aoe and single target (it's our most hatred efficient skill if I'm not mistaken).
I'd change the rune on Prep to Battle Scars again. I think the self heal will help a lot on the harder difficulties. It gives us a little room for mistakes against melee and some more time to nuke down ranged enemies. With just vault (tumbled at that) and caltrops spending discipline, two full globes should suffice for a fight.
As for my PVE build, I really don't have a specific one. There are so many viable options that I don't think there is a one size fit's all PVE build. It's all situational. That being said, almost all of my builds include Caltrops and vault/smokescreen. Usually one aoe hatred spender and one single target hatred spender. Prep is also very strong.
Here are two of my favorites:
Group Grenadier - high hatred generation and focus on spamming powerful spenders. Sentry is there for some group utility while also doing damage.http://us.battle.net/d3/en/calculator/demon-hunter#UPYdZk!geY!accbZc
(Unsure of grenades usefulness other than generating insane amounts of hatred. Also unsure about which rune is best for it. Sentry is more of a filler. I didn't know what else to put there. I was torn between Sentry and Mark of Death.)
A standard solo build - Impale for single targets, multi shot for aoe (thrill of the hunt and multishot roots everything), everything else is self-explanatory.http://us.battle.net/d3/en/calculator/demon-hunter#aZYVdQ!eYZ!aZabba