I've just found the answer:
a for pentane is higher as intermolecular forces in pentane is stronger than those in isopentane.
Pentane and isopentane have the same molecular formula (C5H12), but different in shapes of molecules. Pentane has the shape of "sausage" while isopentane has the shape of a nearly sphere. So, the molecular surface of pentane is larger than those of isopentane. Therefore, the strength of London force in pentane is stronger than in isopentane.
As a result of the difference in shape between the two molecules, pentane has larger molecular size compared to isopentane, therefore b for pentane if higher than b for isopentane.
Thank Borek for your instructions!