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Probability of rolling a 3 is 2/36 & the probability of rolling a 6 is 5/36; probability of rolling a 3 or 5 is 2/36 + 5/36 = 7/36.
On a single roll is it 2/3.
2/36 what you rolled the first time has nothing to do with the next roll. It's an independent event.
The probability of rolling a 3 is 1/6. The probability of rolling a 6 is 1/6. There are two ways to roll a 3 and 6: roll 3 on the first die and 6 on the second or roll 6 on the first and 3 on the second. The probability of the first is 1/6 x 1/6 = 1/36. Likewise the probability of the second is 1/6 x 1/6 = 1/36. Combined you get 1/36 + 1/36 = 2/36 = 1/18
If you roll the die often enough the probability is near enough 1 so as to make no difference. On a single roll, the probability is 1/2.