In organic compounds, the boiling point is affected by the branching and length of the molecules.
The longer and less branched the molecules, the higher the boiling point. The shorter and more branched the molecules, the lower the boiling point.
Let’s look at the structures of each compound mentioned:
Pentane- CH_3(CH_2)_3CH_3
2,2-Dimethylpropane- C(CH_3)_4
As we can see, pentane has fewer branches and a longer chain, this causes a higher amount of induced dipoles, which is the perfect formula for a higher boiling point in comparison to its relevant isomer.