We aim here at analyzing the fundamental properties of positive semidefinite Schrödinger operators on networks. We show that such operators correspond to perturbations of the combinatorial Laplacian through 0-order terms that can be totally negative on a proper subset of the network. In addition, we prove that these discrete operators have analogous properties to the ones of elliptic second order operators on Riemannian manifolds, namely the monotonicity, the minimum principle, the variational treatment...