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http://steamcommunity.com/id/krono-tek/games/?tab=all
What is your antivirus program ? If it is on this list, along with any other anti-intrusion software listed, then it is surely suspect as to your missing .exe error.
https://support.steampowered.com/kb_article.php?ref=9828-SFLZ-9289
Just to clarify, did you add a key of the game on Steam or did you actually buy it on Steam from the Steam store ?
Hopefully, you have a clean installating of the Steam client there as of now from all the troubleshooting you have done and from any damage AVG may have done at this time also.
If you can launch the Steam client and log in normally, then continue here below, please....
That is almost surely your issue or part of it, AVG. I have seen several users here lately report new issues with AVG and Steam. It seems a new update to either of the two is causing more of a conflict now
I say "more" because AVG was already on the list, in bold, and with a green symbol here...
https://support.steampowered.com/kb_article.php?ref=9828-SFLZ-9289
Try the steps in order for AVG..
1. Real-time scan exceptions for Steam and games. Verify game cache, test again.
2. Disable AVG. Verify game cache, test again.
3. Fully uninstall AVG, reboot your computer, verify game cache, test again.
Verify the game cache of New Vegas as suggested here...
https://support.steampowered.com/kb_article.php?ref=2037-QEUH-3335
You have to verify the game cache after each step above and BEFORE you try to playtest the game.
https://support.steampowered.com/kb_article.php?ref=3134-TIAL-4638
According to your profile, you have 50 games.
http://steamcommunity.com/id/krono-tek/games/?tab=all
Here you are saying that you only show 43, so that sounds like you don't have the full list showing in your library for some reason.
Did you go through all the tabs under "Library" in the top of the client and make sure you don't see it anywhere ?
NV also shows that you have 12.9 hours as played but from your words here in the thread, it seemed that you said you just got the game. So how did you get 12.9 hours in it ?
Do you have the game folder in your common folder for FO NV right now and are there files in the folder ?
Don't forget to get a good antivirus program and I don't suggest any that are on that list.
Thanks for replying back as to what the issue was and we are happy you figured it out. Good luck to you always.