Please use code tags. To do this, put [ c o d e ] [ / c o d e ] around your code. It makes it easier for us to read.
Seems like you need to put that randomizing code into a loop...
int[] numOccurrence = new int[12];
for (int i = 0; i < iRollcount; ++i)
++numOccurence[randGen.Next(1, 6) + randGen.Next(1, 6)];
double[] percentOccurence = new double[12];
for (int i = 0; i < 12; ++i)
percentOccurence[i] = ((double)numOccurence[i] / (double)iRollCount) * 100d
It makes a little bit more sense to put your occurence count in a dictionary:
Dictionary<int, int> numOccurence = new Dictionary<int, int>();
Dictionary<int, double> percentOccurence = new Dictionary<int, double>();
for (int i = 0; i < iRollcount; ++i)
++numOccurence[randGen.Next(1, 6) + randGen.Next(1, 6)];
foreach (int iNum in numOccurence.Keys)
percentOccurence[iNum] = ((double)numOccurence[iNum] / (double)iRollCount) * 100d
This way you arent wasting the 0 or 1 index for a value that will never happen. Basically a dictionary maps a key object to a value object, the object types defined in the declaration.