There was an update for Network Manager a few days ago. It looked like
that resolved the issue for me, however unfortunately I was mistaken.

My situation:

Running Xubuntu 12.04.3 LTS
[user] = my username
Trying to connect to university wifi with the same authentication - 
WPA2/PEAP/MSCHAPv2
I have the certificate file provided by the university located at 
~/[user]/.cacerts.pem
I have it currently set to hidden. I don't believe that is the problem since I 
was affected by the issue when it was not hidden as well.
I added system-ca-certs=false line to the connection file in 
/etc/NetworkManager/system-connections
I also made sure the connection file has the line 
'ca-cert=/home/[user]/.cacerts.pem'

1. Do you think changing that line to 'ca-cert=~/[user].cacerts.pem'? Would 
that do anything?
2. Also, I just realized I haven't checked whether setting it to un-hidden 
would change anything after the recent Network Manager update. I might try that 
at some point.

Next time it occurs, I'll try to pull up the log file. Need to figure
out how to do that first.

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https://bugs.launchpad.net/bugs/1104476

Title:
  Network manager cannot connect to WPA2/PEAP/MSCHAPv2 network without
  CA_Certificate

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