The electroclinic (EC) effect is the tilt of the optical axis of a liquid crystal in the plane perpendicular to an applied electric field. Chirality plays a key role for its emergence. Based on the molecular and phase symmetry we derive a molecular expression for the EC coefficient, the material property that quantifies the linear coupling between tilt and electric field, in nematic liquid crystals. Modeling the relevant molecular properties (shape, electric dipole moment, and polarizability) with atomic resolution, we calculate the EC coefficient for prototype molecular structures. We demonstrate that molecular chirality, needed for the occurrence of the EC effect in nematics with a uniform director, is not a necessary requirement in the presence of a twisted director. Our results show that in the latter case conformational deracemization, invoked to explain recent experiments, is not the only mechanism.